JP2014221695A - Sealed package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealed package which is obtained by sealing a pair of glass substrates by using a sealing glass material and has satisfactory airtightness and excellent bending strength.SOLUTION: The sealed package includes: the pair of glass substrates opposed to each other; a sealing layer which is disposed between the pair of glass substrates so that the outer peripheral vicinities thereof are sealed thereby and has a picture frame-like shape mainly comprising straight line parts and the thickness equal to or larger than 10 μm; and a sealing region surrounded by the inside surfaces of each of the glass substrates and the sealing layer. The sealing layer is obtained by calcining a sealing material layer comprising a sealing glass material, which contains sealing glass and a laser absorbing material, and a vehicle and laser-firing the calcined sealing material layer. The line width of the sealing layer in the straight line part is made equal to or larger than 150 μm and smaller than 450 μm, the cross sectional area thereof in the thickness direction is made equal to or larger than 800 μmand smaller than 2,000 μm, and a ratio of the line width of the sealing layer to that of the calcined sealing material layer is made equal to or larger than 100% and smaller than 150%.

Description

  The present invention relates to a sealing package, and more particularly to a sealing package in which a pair of glass substrates are sealed with a sealing glass material.

  A flat panel display device (FPD) such as an organic electro-luminescence display (OELD) or a plasma display panel (PDP) has a light emitting element sealed by a glass package in which a pair of glass substrates are sealed. It has a structure. A liquid crystal display (LCD) also has a structure in which liquid crystal is sealed between a pair of glass substrates. Furthermore, solar cells such as organic thin film solar cells and dye-sensitized solar cells also have a structure in which a solar cell element (photoelectric conversion element) is sealed between a pair of glass substrates.

  Sealing glass is preferably used for sealing. For sealing with sealing glass, for example, a sealing material layer including sealing glass is arranged in a frame shape between a pair of glass substrates to form a glass assembly, and this sealing material layer is heated to 400 to 600 ° C. Done. At this time, if the entire glass assembly is heated using a baking furnace, the light emitting element or the like is easily damaged by the heating. For this reason, after the sealing material layer is temporarily fired to obtain a temporary fired layer, application of laser sealing in which only the temporarily fired layer is heated using laser light (sealing laser light) has been studied.

  According to laser sealing, although the thermal influence on the electronic element part such as a light emitting element can be suppressed, there is a drawback that cracks and cracks are likely to occur in the glass substrate and the sealing layer. Furthermore, in order to cope with the reduction in thickness of the sealing glass package that constitutes an FPD, a solar cell, etc., it is required that the gap (gap) between the glass substrates be reduced to, for example, 10 μm or less. Tends to increase the occurrence of cracks and cracks.

  Therefore, Patent Document 1 discloses a glass member with a sealing material layer that can suppress the occurrence of defects such as cracks and cracks in the glass substrate and the sealing layer even when the sealing glass package is thinned. An electronic device having a hermeticity and reliability improved by using a glass member with a bonding material layer and a manufacturing method thereof are described.

International Publication No. 2011/001987

However, in the electronic device according to Patent Document 1, even when the occurrence of defects such as cracks and cracks in the glass substrate and the sealing layer can be suppressed during production, it is difficult to say that the bending strength is sufficient in use.
An object of the present invention is to provide a sealed package having a sufficient airtightness and an excellent bending strength in a sealed package in which a pair of glass substrates are sealed with a sealing glass material.

The present invention provides a sealing package having the following configuration.
A pair of glass substrates facing each other;
A frame shape mainly consisting of a straight portion, and a sealing layer having a thickness of 10 μm or less, disposed so as to seal the vicinity of the outer periphery between the pair of glass substrates;
A sealing region surrounded by inner surfaces of the glass substrate and the sealing layer, and
A sealing package comprising:
The sealing layer is a layer obtained by pre-baking a sealing material layer comprising a sealing glass and a laser absorber and a sealing material layer composed of a vehicle to obtain a pre-firing layer, followed by laser firing,
The line width of the sealing layer in the linear portion is 150 μm or more and less than 450 μm, the cross-sectional area in the thickness direction is 800 μm ² or more and less than 2000 μm ² , and the ratio of the line width of the sealing layer to the line width of the pre-fired layer Is a sealed package which is 100% or more and less than 150%.

  According to the present invention, in a sealed package in which a pair of glass substrates is sealed with a sealing glass material, it is possible to provide a sealed package having sufficient airtightness and excellent bending strength.

It is a front view of the sealing package by embodiment of this invention. It is sectional drawing along the AA line of the sealing package shown in FIG. It is sectional drawing at the time of lamination | stacking of the 2nd glass substrate with a temporary baking layer and 1st glass substrate in the manufacture process of the sealing package shown in FIG. It is sectional drawing at the time of the laser irradiation in the manufacturing process of the sealing package shown in FIG. It is a schematic sectional drawing which shows the measuring method of the 4-point bending strength in an Example.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. However, the sealing package of the present invention is not limited to this. 1 and 2 are diagrams showing a configuration of a sealing package according to an embodiment of the present invention, and FIGS. 3A and 3B are diagrams showing a manufacturing process of the sealing package according to an embodiment of the present invention.

  The sealing package 1 shown in FIG. 1 and FIG. 2 is an illuminating device (OEL illumination or the like) using a light emitting element such as an FPD such as an OELD, PDP, or LCD, or an OEL element, or a sun such as a dye-sensitized solar cell. It constitutes a battery or the like. The sealing package 1 has a rectangular shape, the same size, the first glass substrate 2 and the second glass substrate 3, and the vicinity of the outer periphery between the first and second glass substrates 2 and 3. A frame-shaped sealing layer 6 is provided.

  FIG. 1 is a front view of the sealing package 1 as viewed from the second glass substrate 3 side, and FIG. 2 is a cross-sectional view taken along line AA of the sealing package shown in FIG. As shown in FIG. 1, the sealing layer 6 is a substantially rectangular frame-shaped layer having four sides formed in a straight line and four corners formed in a curved line. Here, the sealing layer 6 is a layer obtained by calcining a sealing material layer made of a sealing glass material including a sealing glass and a laser absorbing material and a vehicle by pre-firing to make a pre-firing layer. is there. Although details of the manufacturing method of the sealing package will be described later, the laser firing is performed by laser irradiation while scanning along the shape of the temporary firing layer. Usually, the pre-fired layer is composed of a straight portion and a curved portion so that a scanning line of laser irradiation can be drawn smoothly. Therefore, in the sealing package 1, the sealing layer 6 has a configuration in which the main portion is formed by the straight portion 6a and the curved portion 6b is connected between the straight portions 6a. In addition, the shape of the sealing layer in the sealing package of this invention will not be limited to the shape of the sealing layer 6 in the sealing package 1 of this embodiment, if it is a frame shape mainly having a linear part. In addition, the fact that the sealing layer is mainly composed of the straight portion means that the total length of the straight portion is 50% or more of the entire circumference (outer periphery) of the sealing layer.

  In the cross-sectional view of the sealing package 1 shown in FIG. 2, the thickness of the sealing layer 6 indicated by T is 10 μm or less, and the inner surfaces of the first and second glass substrates 2 and 3, that is, facing each other. A region surrounded by the inner surfaces of the surfaces 2 a and 3 a and the sealing layer 6 is a sealing region 5. The thickness of the sealing layer in the sealing package of the present invention is appropriately set to 10 μm or less depending on the type and application of the sealing package. The thickness of the sealing layer is preferably 8 μm or less. Although it depends on the structure of the sealing package, it is preferable that the thickness of the sealing layer is practically 2 μm or more.

  An electronic element unit 4 corresponding to the sealing package 1 is provided in the sealing region 5. The electronic element unit 4 is, for example, an OEL element for OELD or OEL illumination, a plasma light-emitting element for PDP, a liquid crystal display element for LCD, and a dye-sensitized solar cell element (dye-sensitized type for solar cells). Photoelectric conversion element). The electronic element unit 4 including a light emitting element such as an OEL element, a dye-sensitized solar cell element, and the like has various known structures. The sealing package 1 of this embodiment is not limited to the element structure of the electronic element unit 4.

  In the sealing package 1 shown in FIG. 1, the first glass substrate 2 constitutes an element glass substrate, and an element structure such as an OEL element or a PDP element is formed as an electronic element portion 4 on the surface thereof. . The second glass substrate 3 constitutes a glass substrate for sealing the electronic element part 4 formed on the surface of the first glass substrate 2. However, the configuration of the sealing package 1 is not limited to this. For example, when the electronic element unit 4 is a dye-sensitized solar cell element or the like, a wiring film or an electrode film that forms an element structure on each of the surfaces 2a and 3a of the first and second glass substrates 2 and 3 is used. An element film is formed. An element film constituting the electronic element unit 4 and an element structure based thereon are formed on at least one of the surfaces 2a and 3a of the first and second glass substrates 2 and 3.

When an OEL element or the like is applied as the electronic element unit 4, a partial space remains between the first glass substrate 2 and the second glass substrate 3. Such a space may be left as it is, or may be filled with a transparent resin or the like. The transparent resin may be adhered to the glass substrates 2 and 3 or may simply be in contact with the glass substrates 2 and 3. When a dye-sensitized solar cell element or the like is applied as the electronic element unit 4, the electronic element unit 4 is disposed in the entire gap between the first glass substrate 2 and the second glass substrate 3. .
In addition, the object which the sealing package of this invention seals in the inside is not limited to an electronic element part, For example, a photoelectric conversion apparatus etc. may be sufficient. Alternatively, the sealing package of the present invention may be a glass member (such as a building material) that does not have an electronic element portion or the like in a sealing region such as a multilayer glass.

  In the sealing package 1 shown in FIGS. 1 and 2, the line width at the straight portion 6 a of the sealing layer 6 is indicated by Wa. The line width in the straight part of the sealing layer in the sealing package of the present invention is 150 μm or more and less than 450 μm, and therefore the line width Wa of the sealing layer 6 in the sealing package 1 is within the range in all the linear parts 6a. . Thus, in this specification, the line width in the straight part of the sealing layer being 150 μm or more and less than 450 μm means that the line width of the sealing layer is 150 μm or more and less than 450 μm in all the straight parts. Say. That is, in the sealing package of the present invention, the line width of the linear portion of the sealing layer is 150 μm or more at the smallest portion and less than 450 μm at the largest portion.

  Hereinafter, when the range of the cross-sectional area in the thickness direction in the linear portion of the sealing layer and the range of the ratio of the line width of the sealing layer to the line width of the pre-fired layer are similarly defined, The range is applied at the straight portion. In addition, about the measuring method of the thickness (film thickness) and the line width of each of the pre-fired layer and the sealing layer, a measuring method usually applied to the sealing package can be applied without particular limitation. For example, the film thickness of the pre-fired layer is measured by a scanning electron microscope or a surface roughness / contour measuring instrument, and the line width of the pre-fired layer is measured by a metal microscope, a laser microscope, or a surface roughness measuring / contour measuring instrument. Etc. can be measured. The film thickness of the sealing layer can be measured by a scanning electron microscope or the like, and the line width of the sealing layer can be measured by a metal microscope, a laser microscope or the like.

  In this specification, unless the thickness (film thickness) and the line width of the temporary fired layer and the sealing layer are otherwise specified, the thickness of the temporary fired layer is measured by a surface roughness / contour shape measuring instrument. The line width is a value measured by a metallographic microscope, the film thickness of the sealing layer is measured by a scanning electron microscope, and the line width of the sealing layer is a value measured by a metallographic microscope.

  When the line width of the sealing layer is 450 μm or more in any part of the linear part, stress due to the difference in thermal expansion between the sealing glass material and the glass substrate including the sealing glass and the laser absorbing material increases, and sealing is performed. A sufficient bending strength cannot be obtained in the package. It is preferable that the line width in the straight part of the sealing layer is less than 400 μm in any part.

  When the line width in the straight part of the sealing layer is less than 150 μm at any part, the strength of the sealing layer is weak and sufficient bending strength cannot be obtained in the sealing package. The line width at the straight portion of the sealing layer is preferably 200 μm or more in any portion, and more preferably 250 μm or more.

In the sealing package 1, the cross-sectional area in the thickness direction of the straight portion 6a of the sealing layer 6 is indicated by S in FIG. The cross-sectional area S in the thickness direction can be calculated by the thickness T × the line width Wa of the sealing layer 6 as shown in FIG. The cross-sectional area in the thickness direction of the linear portion of the sealing layer in the sealing package of the present invention is 800 μm ² or more and less than 2000 μm ² . Therefore, the cross-sectional area S in the thickness direction of the sealing layer 6 in the sealing package 1 is within the range of all the straight portions 6a. Note that the thickness of the sealing layer in the sealing package is appropriately set to 10 μm or less depending on the type and application of the sealing package. Therefore, the adjustment of the cross-sectional area in the thickness direction of the sealing layer is performed by adjusting the line width within the above range so that the above range is obtained at the set thickness.

When the cross-sectional area in the thickness direction of the sealing layer is 2000 μm ² or more in any part of the linear portion, the stress due to the difference in thermal expansion between the sealing glass material including the sealing glass and the laser absorbing material and the glass substrate is It increases, and sufficient bending strength cannot be obtained in the sealed package. Sectional area in the thickness direction of the linear portion of the sealing layer is preferably 1950Myuemu ² or less in any of the portions, more preferably 1900Myuemu ² or less.

If the cross-sectional area in the thickness direction at the straight part of the sealing layer is less than 800 μm ² at any part, the strength of the sealing layer is weak and sufficient bending strength cannot be obtained in the sealing package. The cross-sectional area in the thickness direction of the linear portion of the sealing layer is preferably 1000 μm ² or more in any portion.

  Furthermore, the ratio of the line width of the sealing layer to the line width of the temporarily fired layer in the linear portion of the sealing layer in the sealing package of the present invention is 100% or more and less than 150%.

  The sealing layer is a layer obtained by pre-baking a sealing material layer including a sealing glass and a laser absorber containing a sealing glass material and a vehicle to obtain a pre-sintered layer, followed by laser baking. FIG. 3A is a cross-sectional view of the second glass substrate 3 with the provisional fired layer 7 and the first glass substrate 2 on which the electronic element portion 4 is disposed in the manufacturing process of the sealing package 1. FIG. 3B shows a cross-sectional view when the pre-fired layer 7 in the laminated body obtained by laminating as shown in FIG. 3A is fired by laser irradiation.

As shown in FIG. 3A, the sealing package 1 is produced by, for example, first attaching a provisional firing layer 7 obtained by provisionally firing a sealing material layer formed in a frame shape on the surface 3a of the second glass substrate 3. 2 and the first glass substrate 2 in which the electronic element part 4 is disposed on the surface 2a are used.
After laminating the first glass substrate 2 and the second glass substrate 3 such that the surfaces 2a and 3a face each other, as shown in FIG. 3B, the temporary fired layer is interposed through the second glass substrate 3. 7 is irradiated with the laser beam 10, whereby the temporarily fired layer 7 is melted and solidified by the heat of the laser beam to form the sealing layer 6. The temporary fired layer 7 is fixed to the first glass substrate 2 when melted and solidified, and the second glass substrate 3 and the first glass substrate 2 are sealed through the sealing layer 6 and hermetically sealed. .

  3A and 3B are cross-sectional views corresponding to the AA cross section in FIG. In FIG. 3A, the line width at the straight line portion of the pre-fired layer 7 is denoted by Wb. As described above, the ratio of the line width of the sealing layer to the line width of the temporarily fired layer in the linear portion of the sealing layer in the sealing package of the present invention is 100% or more and less than 150%. Therefore, the ratio of the line width Wa of the sealing layer 6 to the line width Wb of the pre-fired layer 7 when the sealing package 1 is manufactured is within the range of all the straight portions. Hereinafter, for example, the ratio (%) of the line width of the sealing layer to the line width of the temporarily fired layer represented by Wa / Wb × 100 is referred to as the sealing ratio of the sealing layer as necessary.

  When the sealing ratio of the sealing layer is less than 100% at any part of the linear portion, the adhesion strength between the sealing layer and the glass substrate is insufficient, and when the sealing package is bent, the sealing layer and the glass substrate Sufficient bending strength cannot be obtained, such as peeling from the interface. It is preferable that the sealing ratio in the straight part of the sealing layer is 110% or more in any part.

  If the sealing ratio of the sealing layer is 150% or more in any part of the linear portion, cracks are likely to occur in the glass substrate and sealing layer around the sealing layer due to thermal stress during laser firing, and sufficient airtightness And bending strength cannot be obtained. The sealing ratio in the straight part of the sealing layer is preferably 140% or less in any part, more preferably 130% or less.

  In the sealing package of the present invention, the adhesive strength between the sealing layer and the glass substrate is sufficiently obtained by setting the line width, the cross-sectional area in the thickness direction, and the sealing ratio in the straight portion of the sealing layer within the above ranges. While holding, the bending stress of the sealing package can be improved to a sufficient level by reducing the thermal stress due to the difference in thermal expansion between the glass material for sealing and the glass substrate generated during laser firing.

  As long as the straight part of the sealing layer satisfies the above conditions, the curved part formed continuously from the straight part has the same thickness as the straight part, but the line width and cross-sectional area are particularly limited. Not. However, since the linear portion and the curved portion of the sealing layer are not formed individually but continuously, the line width is not greatly different between the linear portion and the curved portion. Preferably, the line width, the cross-sectional area in the thickness direction, and the sealing ratio in the same range as the straight line portion are also applied to the curved portion.

  The size of the sealing region in the sealing package according to the embodiment of the present invention is appropriately adjusted according to the size of a member such as an electronic element to be sealed. Furthermore, the size of the sealing package is appropriately adjusted according to the required size of the sealing region. In the sealed package of the present invention, like the sealed package 1 shown in FIG. 1, the pair of glass substrates is rectangular, and the length of the diagonal line (shown by X in FIG. 1) is 4 inches or more. In some cases, a significant effect is exerted particularly on the bending strength. Also, depending on the structure of the sealed package, if the present invention is applied, a practically sufficient bending strength can be imparted to the sealed package whose diagonal length of the glass substrate is approximately 55 inches at maximum. Furthermore, depending on the structure of the sealed package, if the present invention is applied, a practically sufficient bending strength can be imparted to a small-sized sealed package having a diagonal length of about 2 inches on the glass substrate. it can.

In the sealing package 1 shown in FIG. 1, the first and second glass substrates 2 and 3 are made of, for example, alkali-free glass or soda lime glass having various known compositions. In one sealing package, the first glass substrate and the second glass substrate are usually made of the same type of glass. The alkali-free glass has a thermal expansion coefficient of about 35 to 40 × 10 ⁻⁷ / ° C. (50 to 250 ° C.). Soda lime glass has a thermal expansion coefficient of about 80 to 90 × 10 ⁻⁷ / ° C. (50 to 250 ° C.). The temperature range shown in parentheses after the thermal expansion coefficient is the temperature range when the thermal expansion coefficient is measured. In this specification, unless otherwise specified, the thermal expansion coefficient indicates a thermal expansion coefficient in a temperature range of 50 to 250 ° C.

  In addition, the sealing layer 6 is obtained by temporarily firing a sealing material layer composed of a sealing glass material and a laser absorbing material and a vehicle to form a temporary firing layer 7 shown in FIG. As shown, it is a layer obtained by laser firing.

  The glass material for sealing contains sealing glass as a main component and a laser absorber which is an essential component for performing laser firing. Sealing glass materials usually further contain a low expansion filler to adjust the coefficient of thermal expansion. Both the laser absorber and the low expansion filler function as fillers. Hereinafter, these may be collectively referred to as a filler. Moreover, the glass material for sealing may contain additives other than these as needed.

Sealing glass is usually used as a glass frit. The average particle diameter (D50) of the glass frit used as the sealing glass is preferably about 0.1 to 2.0 μm.
As the sealing glass, for example, low-melting glass such as tin-phosphate glass, bismuth glass, vanadium glass, and lead glass is used. Of these, tin-phosphate glass is used in consideration of sealing properties (adhesiveness) to the glass substrates 2 and 3, reliability thereof (adhesion reliability and sealing properties), and influence on the environment and human body. It is preferable to use sealing glass made of bismuth glass, and bismuth glass is particularly preferable.

Tin-phosphate glass used as sealing glass is 20 to 68% by mass of SnO, 0.5 to 5% by mass of SnO ₂ , and 20 to 40% by mass of P ₂ O ₅ (basically total The composition is preferably 100% by mass. SnO is a component for lowering the melting point of glass. If the SnO content is less than 20% by mass, the viscosity of the glass becomes high and the sealing temperature becomes too high.

The tin-phosphate glass formed with the above three components has a low glass transition point and is suitable for a low-temperature sealing material, but a component that forms a glass skeleton such as SiO ₂ , ZnO, _{B 2 O 3, Al 2 O} 3, WO 3, MoO 3, Nb 2 O 5, TiO 2, ZrO 2, Li 2 O, Na 2 O, K 2 O, Cs 2 O, MgO, CaO, SrO, BaO A component that stabilizes glass or the like may be contained as an optional component. However, if the content of the optional component is too large, the glass becomes unstable and devitrification occurs, and the glass transition point and softening point may increase. Therefore, the total content of the optional component is 30% by mass. The following is preferred. The glass composition in this case is adjusted so that the total amount of the basic component and the optional component is basically 100% by mass.
In addition, the thermal expansion coefficient of the tin-phosphate glass having the above composition is approximately 110 to 160 × 10 ⁻⁷ / ° C.

The bismuth-based glass used as the sealing glass is 70 to 90% by mass of Bi ₂ O ₃ , 1 to 20% by mass of ZnO, and 2 to 12% by mass of B ₂ O ₃ (basically, the total amount is 100 It is preferable to have a composition of (mass%). Bi ₂ O ₃ is a component that forms a glass network. When the content of Bi ₂ O ₃ is less than 70% by mass, the softening point of the low-melting glass becomes high and sealing at a low temperature becomes difficult. When the content of Bi ₂ O ₃ exceeds 90% by mass, it becomes difficult to vitrify and the thermal expansion coefficient tends to be too high.

ZnO is a component that lowers the thermal expansion coefficient and the like. Vitrification becomes difficult when the content of ZnO is less than 1% by mass. When the content of ZnO exceeds 20% by mass, stability during low-melting glass molding is lowered, and devitrification is likely to occur. B ₂ O ₃ is a component that forms a glass skeleton and widens the range in which vitrification is possible. When the content of B ₂ O ₃ is less than 2% by mass, vitrification becomes difficult, and when it exceeds 12% by mass, the softening point becomes too high, and even if a load is applied during sealing, sealing is performed at a low temperature. It becomes difficult.

The bismuth-based glass formed from the above three components has a low glass transition point and is suitable for a sealing material for low temperature. Al ₂ O ₃ , CeO ₂ , SiO ₂ , Ag ₂ O, MoO ₃ , _{nb 2 O 3, Ta 2 O} 5, Ga 2 O 3, Sb 2 O 3, Li 2 O, Na 2 O, K 2 O, Cs 2 O, CaO, SrO, BaO, WO 3, P 2 O 5, An optional component such as SnO _x (x is 1 or 2) may be contained. However, if the content of any component is too large, the glass becomes unstable and devitrification may occur, and the glass transition point and softening point may increase. Therefore, the total content of any component is 30% by mass. The following is preferable. The glass composition in this case is adjusted so that the total amount of the basic component and the optional component is basically 100% by mass.
The thermal expansion coefficient of the bismuth glass having the above composition is approximately 85 to 115 × 10 ⁻⁷ / ° C.

  As the laser absorber contained in the glass material for sealing as an essential component, at least one metal selected from Fe, Cr, Mn, Co, Ni and Cu or a compound such as an oxide containing the metal is used. The laser absorbing material may be a pigment other than these.

  In addition, about the particle size of a laser absorber, it is calculated | required that the maximum particle size is at least less than the thickness of a temporary baking layer. Although the film thickness is reduced by laser firing, the reduction rate is small, so the thickness of the temporary fired layer may be about 100 to 120% of the thickness of the sealing layer to be obtained. Therefore, the thickness of the temporarily fired layer is approximately 12 μm or less. In order to produce a calcination layer having such a thickness, the particle diameter of the laser absorber is preferably about 1 to 10 μm as Dmax. In addition, as an average particle diameter (D50) of a laser absorber, 0.1-2.0 micrometers is preferable in general.

  The content of the laser absorber is preferably in the range of 2 to 10% by volume with respect to the total amount of the glass material for sealing. If the content of the laser absorber is less than 2% by volume, the pre-fired layer may not be sufficiently melted during laser irradiation. This causes poor adhesion. On the other hand, when the content of the laser absorbing material exceeds 10% by volume, heat is locally generated near the interface between the glass substrate on the irradiation side during laser irradiation, in FIG. 3B, the second glass substrate 3 and the pre-fired layer. There is a possibility that the glass substrate (second glass substrate 3) on the irradiation side is cracked. Moreover, the fluidity at the time of melting of the glass material for sealing deteriorates, and there is a possibility that the adhesiveness between the glass substrate opposite to the laser irradiation side, that is, the first glass substrate 2 and the sealing layer in FIG. .

As the low expansion filler optionally contained in the sealing glass material, at least one selected from silica, alumina, zirconia, zirconium silicate, cordierite, zirconium phosphate compound, soda lime glass, and borosilicate glass is used. It is preferable. Examples of the zirconium phosphate-based compound include (ZrO) ₂ P ₂ O ₇ , NaZr ₂ (PO ₄ ) ₃ , KZr ₂ (PO ₄ ) ₃ , Ca _0.5 Zr ₂ (PO ₄ ) ₃ , and NbZr (PO ₄ ). ₃ , Zr ₂ (WO ₃ ) (PO ₄ ) ₂ , and composite compounds thereof.
The particle size of the low expansion filler can be the same as the particle size of the laser absorber described above.

The low expansion filler has a lower thermal expansion coefficient than that of the sealing glass, and the thermal expansion coefficient is about −15 to 45 × 10 ⁻⁷ / ° C. In the glass material for sealing, the low expansion filler is contained for the purpose of reducing the thermal expansion coefficient of the entire glass material for sealing. The laser absorbing material, which is an essential component, has various thermal expansion coefficients depending on the type. Therefore, the content of the low expansion filler in the sealing glass material is adjusted in consideration of the type and composition of the laser absorber used in the required thermal expansion coefficient of the sealing glass material.

In sealing packages of the present invention, the thermal expansion coefficient of the glass substrate and the thermal expansion coefficient of the sealing glass material as alpha ₁ used for forming the sealing layer when the alpha _2, sealing represented by alpha _{1-.alpha. 2} The difference in thermal expansion coefficient between the wearing glass material and the glass substrate is preferably 15 to 65 × 10 ⁻⁷ / ° C. Hereinafter, the difference in the thermal expansion coefficient is referred to as a thermal expansion difference (α ₁ −α ₂ ) as necessary.

Here, cracks and cracks in the glass substrate and the sealing layer at the time of laser firing are caused by residual stress σ (determined by the following formula (1)) generated in the glass substrate as the temporary fired layer is melted and solidified.
σ = α · ΔT · E / (1-ν) (1)

However, in Formula (1), (alpha) is a thermal expansion difference ((alpha) _1- (alpha) ₂ ) of the glass material and glass substrate for sealing, and (DELTA) T is a normal temperature from the temperature difference at the time of laser baking (melting temperature (baking temperature) of a temporary baking layer). (Temperature difference until cooling to the vicinity) divided by cooling time, E is the Young's modulus of the glass material or glass substrate for sealing, and ν is the Poisson's ratio. In the case of laser firing, if the scanning speed and spot diameter of the laser light are constant, the cooling time is almost constant, so ΔT is substantially the temperature difference during laser firing.

In the sealed package of the present invention, since the temporary fired layer is thin, α and ΔT, which are elements for reducing the residual stress σ in Equation (1), are in a competing relationship. That is, if the content of the filler of the glass material for sealing is increased in order to reduce α, the fluidity of the glass material for sealing is lowered. Therefore, in order to increase the fluidity of the glass material for sealing, the temperature of laser firing (heating temperature) must be increased, and the value of ΔT increases accordingly, resulting in an increase in the residual stress σ. Therefore, in the present invention, α (difference in thermal expansion between sealing glass material and glass substrate (α ₁ −α ₂ )) is used as described above so as to keep the value of residual stress σ small by balancing α and ΔT. A range is selected.

If the difference in thermal expansion (α ₁ −α ₂ ) between the glass material for sealing and the glass substrate is within the above range, the content of the low expansion filler in the glass material for sealing is reduced to improve the fluidity of the glass material for sealing. By maintaining and lowering the laser firing temperature (heating temperature) based on this, the residual stress at the time of laser firing is reduced, so that it becomes possible to suppress cracks and cracks in the glass substrate and the sealing layer.

That is, when the difference in thermal expansion (α ₁ −α ₂ ) between the glass material for sealing and the glass substrate is less than 15 × 10 ⁻⁷ / ° C., the glass material for sealing contains a relatively large amount of filler and further filled. When the particle size of the material is a fine particle size applicable to the thickness of the pre-baked layer, the fluidity of the material is lowered, so that an increase in the laser baking temperature is inevitable.

The total of the low expansion filler and the laser absorber in the sealing glass material when the difference in thermal expansion (α ₁ −α ₂ ) between the sealing glass material and the glass substrate is 15 × 10 ⁻⁷ / ° C. About 44 volume% is mentioned as content. That is, if the total content of the low expansion filler and the laser absorber is 44% by volume or less, the effect of lowering the laser firing temperature (heating temperature) can be sufficiently obtained. Here, since the content of the laser absorber is preferably 2 to 10% by volume as described above, the content of the low expansion filler is preferably 42% by volume or less with respect to the sealing glass material.

Moreover, when the thermal expansion difference (α ₁ −α ₂ ) between the glass material for sealing and the glass substrate exceeds 65 × 10 ⁻⁷ / ° C., the shrinkage amount between the glass substrate and the pre-fired layer is affected by the laser firing temperature. Since the influence of the difference becomes large, even if the laser firing temperature is lowered, the glass substrate or the sealing layer is likely to be cracked or broken.

Thus, if the thermal expansion difference (α ₁ -α ₂ ) between the sealing glass material and the glass substrate is in the range of 65 × 10 ⁻⁷ / ° C. or less, the inclusion of the low expansion filler in the sealing glass material The amount can be reduced. Furthermore, even if the glass material for sealing does not contain a low expansion filler, the difference in thermal expansion (α ₁ −α ₂ ) between the glass material for sealing and the glass substrate may be 65 × 10 ⁻⁷ / ° C. or less. For example, it becomes possible to suppress cracks and cracks in the glass substrate and the sealing layer. The glass material for sealing should just contain the laser absorber as a filler at least, and content of a low expansion | swelling filler may be zero. For this reason, the total content of the low expansion filler and the laser absorber may be 2% by volume or more which is the lower limit value of the content of the laser absorber.

However, in reducing the difference in shrinkage between the glass substrate and the temporary firing layer during laser firing, the difference in thermal expansion (α ₁ −α ₂ ) between the glass material for sealing and the glass substrate is 50 × 10 ⁻⁷ / It is preferable to set it as ° C or less, and it is more preferable to set it as ^35x10-7 / C or less. From such a point, it is preferable that the glass material for sealing contains a low expansion filler in the range of 10 volume% or more. According to the sealing glass material containing these fillers in the range of 2 to 10% by volume of the laser absorber, 10 to 42% by volume of the low expansion filler, and 2 to 44% by volume as the total amount of both. The laser firing temperature can be lowered while reducing the difference in shrinkage between the glass substrate and the pre-fired layer at the time of laser firing, which contributes to improving the reliability of the sealing property.

Here, the fluidity of the glass material for sealing in the pre-fired layer and the laser firing temperature based thereon are not only the content of the filler (laser absorber or low expansion filler) in the glass material for sealing, but also the filler. It is also affected by the particle shape. As described above, it is necessary that the filler particles have at least the maximum particle size less than the thickness of the pre-fired layer. In addition, it is preferable to reduce the specific surface area of the filler particles. Specifically, the filler preferably has a surface area per unit volume of the sealing glass in the range of 0.5 to 6 m ² / cm ³ .

  The surface area of the filler in the glass material for sealing is a value represented by [(specific surface area of filler) × (specific gravity of filler) × (content of filler (volume%)]. When a filler consists of a laser absorber and a low expansion filler, it can be set as the surface area of a filler by totaling the surface area calculated | required about each of a laser absorber and a low expansion filler.

By setting the surface area of the filler relative to the unit volume of the sealing glass to be in the range of 0.5 to 6 m ² / cm ³ , the fluidity of the glass material for sealing can be further improved, and the laser firing temperature can be further reduced. . The surface area of the filler particles described above can be satisfied by controlling the particle size distribution of the low expansion filler or the laser absorber. Specifically, when preparing a low expansion filler or a laser absorbing material, each powder can be obtained by classification by sieving or wind separation.

The sealing package of the present invention has been described above. Below, the sealing package 1 mentioned above is demonstrated to the example about the manufacturing method of the sealing package of this invention.
First, as shown in FIG. 3A, a second glass substrate 3 with a pre-fired layer 7 obtained by pre-firing a sealing material layer formed in a frame shape on the surface 3a of the second glass substrate 3, and the surface The 1st glass substrate 2 with which the electronic element part 4 was arrange | positioned by 2a is prepared.

In preparing the second glass substrate 3 with the pre-fired layer 7, first, a sealing glass material including a sealing glass and a laser absorbing material described above and a sealing material made of a vehicle are prepared.
As described above, the sealing glass material may contain a low expansion filler in addition to the sealing glass and the laser absorber, and the total content of the low expansion filler and the laser absorber relative to the total amount of the sealing glass material. Is preferably in the range of 2 to 44% by volume. Moreover, the glass material for sealing from which the thermal expansion difference ((alpha) _1- (alpha) ₂ ) with the glass substrates 2 and 3 becomes the range of 15-65 * 10 < ^-7 > / degreeC preferably based on it is prepared.

Next, such a sealing glass material is mixed with a vehicle to prepare a sealing material. The sealing material is usually in a paste form, and is hereinafter also referred to as a sealing material paste.
As the vehicle, for example, a solvent in which a resin as a binder component is dissolved in a solvent is used. Specifically, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, propyl cellulose, nitrocellulose or the like dissolved in a solvent such as terpineol, butyl carbitol acetate, ethyl carbitol acetate, or methyl (meth) Acrylic resin such as acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, etc. dissolved in a solvent such as methyl ethyl ketone, terpineol, butyl carbitol acetate, ethyl carbitol acetate Is mentioned.

  The viscosity of the sealing material paste may be adjusted to the viscosity corresponding to the apparatus applied to the glass substrate 3, and can be adjusted by the ratio of the resin (binder component) and the solvent in the vehicle, and the ratio of the sealing glass material and the vehicle. it can. A known additive may be added to the sealing material paste as a glass paste such as an antifoaming agent or a dispersing agent. A known method using a rotary mixer equipped with a stirring blade, a roll mill, a ball mill or the like can be applied to the preparation of the sealing material paste.

  The sealing material paste described above is applied to the second glass substrate 3 in a frame shape to form a sealing material layer. The sealing material paste is applied so that the film thickness of the sealing layer obtained after laser firing, the line width of the straight portion, and the cross-sectional area in the thickness direction are within the scope of the present invention. For the application of the sealing material paste, for example, a printing method such as screen printing or gravure printing or a coating method using a dispenser can be applied. The sealing material layer obtained by applying the sealing material paste is usually subjected to a subsequent pre-baking step after a drying step of, for example, 10 minutes or more at a temperature of 120 ° C. or higher. A drying process is implemented in order to remove a solvent from a sealing material layer. If the solvent remains in the dried layer of the sealing material obtained by drying, the binder component may not be sufficiently removed in the subsequent pre-baking step.

  The sealing material layer of the above-described sealing material paste is usually calcined through the drying process as described above to form a calcined layer 7. In the pre-baking step, the drying layer of the sealing material is heated to a temperature below the glass transition point of the sealing glass, which is the main component of the sealing glass material, and the binder component in the drying layer is removed. The glass material for sealing is heated and heated to a temperature equal to or higher than the softening point and baked on the glass substrate 3. In this way, the temporary fired layer 7 in which the sealing glass material is baked into a predetermined frame shape is formed on the second glass substrate 3.

  On the other hand, the first glass substrate 2 on which the electronic element portion 4 is disposed on the surface 2a is a sealing package 1 to be produced, for example, an FPD such as an OELD, PDP, or LCD, an illumination device using an OEL element, a dye sensitizer. It is prepared by a conventionally known method in accordance with the specifications of a solar cell such as a sensitive solar cell.

  Subsequently, the sealing package 1 is produced using the 2nd glass substrate 3 with the provisional baking layer 7 produced above, and the 1st glass substrate 2 with the electronic element part 4 produced separately. That is, as shown to FIG. 3A, the 1st glass substrate 2 and the 2nd glass substrate 3 are laminated | stacked through the temporary baking layer 7 so that those surfaces 2a and 3a may oppose. A gap is formed between the first glass substrate 2 and the second glass substrate 3 based on the thickness of the pre-fired layer 7.

  FIG. 3B shows a cross-sectional view when the pre-fired layer 7 in the laminated body obtained by laminating as shown in FIG. 3A is fired by laser irradiation.

  Next, as shown in FIG. 3B, the laser firing process is performed by irradiating the pre-fired layer 7 with the laser light 10 through the second glass substrate 3. The laser beam 10 may be applied to the temporarily fired layer 7 through the first glass substrate 2. The laser beam 10 is irradiated while scanning along the frame-shaped temporary firing layer 7. And the sealing obtained by irradiating the laser beam 10 over the perimeter of the temporary baking layer 7 between the 1st glass substrate 2 and the 2nd glass substrate 3 as shown in FIG.1 and FIG.2. The sealing layer 6 is formed so that the thickness, the line width of the straight portion, the cross-sectional area in the thickness direction, and the sealing ratio are within the scope of the present invention so as to have the region sealed with the layer 6.

  The type of the laser beam 10 is not particularly limited, and a laser beam from a semiconductor laser, a carbon dioxide gas laser, an excimer laser, a YAG laser, a HeNe laser, or the like is used. The conditions for irradiating the laser beam 10 are selected so that the thickness of the sealing layer 6 to be obtained, the line width of the straight portion, the cross-sectional area in the thickness direction, and the sealing ratio are within the scope of the present invention. The output of the laser beam 10 is preferably in the range of 2 to 150 W, for example. If the laser output is less than 2 W, the pre-fired layer 7 may not be melted, and if it exceeds 150 W, cracks and cracks are likely to occur in the glass substrates 2 and 3. The output of the laser beam 10 is more preferably in the range of 5 to 100W.

  In this way, the electronic element portion 4 was hermetically sealed in the sealing region 5 surrounded by the surfaces 2 a and 3 a of the first glass substrate 2 and the second glass substrate 3 and the inner wall surface of the sealing layer 6. The sealing package 1 is produced. According to the sealed package 1 of such an embodiment, it is possible to provide a sealed package having sufficient airtightness and excellent bending strength.

  As mentioned above, although the embodiment of the sealing package of this invention was mentioned giving the example shown by FIG. 1 and FIG. 2, the sealing package of this invention is not limited to these. As long as it does not contradict the spirit of the present invention, the configuration can be changed as necessary.

  Next, specific examples of the present invention and evaluation results thereof will be described. In addition, the following description does not limit this invention, The modification | change in the form along the meaning of this invention is possible. In the following examples, a sealed package 1 having the same configuration as that shown in FIGS. 1 and 2 was produced. Examples 1 to 7 are examples, and examples 8 to 11 are comparative examples.

(Example 1)
Bi ₂ O ₃ 81.8% by mass, B ₂ O ₃ 6.0% by mass, ZnO 10.6% by mass, Al ₂ O ₃ 0.9% by mass, SiO ₂ 0.7% by mass, average A bismuth glass frit (softening point: 410 ° C.) having a particle size (D50) of 0.5 μm, a cordierite powder as a low expansion filler, and a laser absorber having an Fe ₂ O ₃ —CuO—MnO composition are prepared did. The cordierite powder as a low expansion filler has a particle size distribution with D10 of 0.5 μm, D50 of 0.9 μm, D90 of 1.3 μm and Dmax of 1.9 μm, and a specific surface area of 13.2 m ² / g. The laser absorber has a particle size distribution with D10 of 0.4 μm, D50 of 0.8 μm, D90 of 1.2 μm, and Dmax of 2.8 μm, and a specific surface area of 9.2 m ² / g.

Glass material (thermal expansion coefficient α ₁ (50 to 250 ° C.)) for sealing by mixing 69.5% by volume of the bismuth-based glass frit described above, 19.9% by volume of cordierite powder, and 10.6% by volume of the laser absorber. : 80 × 10 ⁻⁷ / ° C.). A sealing material paste was prepared by mixing 80% by mass of the sealing glass material with 20% by mass of the vehicle. The vehicle is obtained by dissolving ethyl cellulose (2.5% by mass) as a binder component in a solvent (97.5% by mass) made of terpineol.

Next, the second glass substrate 3 (dimensions: 57.61 × 81.34 × 0.5 mmt) made of alkali-free glass (thermal expansion coefficient α ₂ (50 to 250 ° C.): 38 × 10 ⁻⁷ / ° C.) A screen mask having a pattern with a line width of 250 μm is used to form a sealing layer forming region in a frame shape having a line center of 79.29 × 56.06 mm and a corner R of 1 mm. Then, a sealing material layer was formed by coating by a screen printing method. The second glass substrate 3 with the sealing material layer was allowed to stand at 120 ° C. for 10 minutes to dry the sealing material layer.

The sealing material layer on the second glass substrate 3 is dried under the above conditions, and then calcined under conditions of 500 ° C. × 10 minutes, whereby a calcined layer having a film thickness of 4.0 μm and a line width of 280 μm. 7 was formed. Difference between the thermal expansion coefficient α ₁ (80 × 10 ⁻⁷ / ° C.) of the sealing glass material used for forming the pre-fired layer 7 and the thermal expansion coefficient α ₂ (38 × 10 ⁻⁷ / ° C.) of the glass substrate ( α ₁ −α ₂ ) is 42 × 10 ⁻⁷ / ° C.

The second glass substrate 3 having the pre-fired layer 7 and the first glass substrate 2 having the element region (region in which the OEL element 4 is formed) (the same composition and the same shape as the second glass substrate 3). A substrate made of glass). Next, a laser beam (semiconductor laser) having a wavelength of 940 nm, an output of 40 W, and a spot diameter of 1.6 mm is irradiated to the temporary fired layer 7 through the second glass substrate 3 at a scanning speed of 10 mm / s. The first glass substrate 2 and the second glass substrate 3 were sealed as the sealing layer 6 by melting and rapidly cooling and solidifying. The processing (firing) temperature (measured with a radiation thermometer) at the time of laser irradiation was 785 ° C. In the layer obtained by laser firing the pre-fired layer 7, that is, the sealing layer 6, the film thickness is 3.3 μm, the line width of the straight part is 342 μm, the cross-sectional area in the thickness direction of the straight part is 1129 μm ² , The sealing ratio of the part was 122%. In this manner, a sealing package A as an electronic device in which the element region was sealed with a pair of glass substrates and a sealing layer was produced.

  In addition, the film thickness of the sealing layer 6 and the line width of the straight line part were average values of numerical values measured at the central parts of the four sides formed by the straight line part 6a as shown in FIG. The film thickness of the pre-fired layer 7 and the line width of the linear portion are also values measured and calculated in the same manner at the linear portion corresponding to the linear portion 6a of the sealing layer 6 shown in FIG. Here, the film thickness of the pre-fired layer 7 was measured with a surface roughness / contour shape measuring instrument (Tokyo Seimitsu Surfcom 1400D), and the line width of the straight portion of the pre-fired layer 7 was measured with a metal microscope (OLYMPUS BX51). Moreover, the film thickness of the sealing layer 6 was measured with the scanning electron microscope (JEOL JSM-646OLA), and the line | wire width of the linear part of the sealing layer 6 was measured with the metal microscope (OLYMPUS BX51), respectively. The sealing ratio of the linear portion of the sealing layer 6 was calculated as the line width of the sealing layer 6 measured / calculated above / the line width of the pre-fired layer 7 × 100.

  When the sealing ratio is 100% or more, the cross-sectional area in the thickness direction at the straight portion of the sealing layer 6 is equal to the line width of the sealing layer 6 in the average value of the film thickness of the sealing layer 6 obtained above. It is a value calculated by multiplying the average value. In the case where the sealing ratio is less than 100%, the cross-sectional area in the thickness direction of the linear portion of the sealing layer 6 is the average value of the line width of the temporarily fired layer 7 to the average value of the film thickness of the temporarily fired layer 7. The value calculated by multiplying by.

Table 1 shows the glass materials used for sealing and the thermal expansion coefficients α ₁ and α _{2 of the} glass substrate, and the manufacturing conditions, the pre-fired layer, the film thickness of the sealing layer, the line width of the straight part, and the thickness direction of the straight part. The cross-sectional area and the seal ratio of the straight portion are shown.

(Example 2)
A sealing package in which the film thickness of the sealing layer, the line width of the straight part, the cross-sectional area in the thickness direction of the straight part, and the sealing ratio of the straight part are changed in the same manner as in Example 1 except that the laser output is 38 W B was produced. The thermal expansion coefficients α ₁ and α _{2 of} the glass material used for sealing and the glass substrate used in Table 1, and the production conditions, the pre-fired layer, the film thickness of the sealing layer, the line width of the linear portion, and the thickness direction of the linear portion The cross-sectional area and the seal ratio of the straight part are shown.

(Example 3)
Adjust the screen printing conditions to adjust the film thickness of the pre-fired layer as shown in Table 1, and further adjust the laser output to adjust the film thickness of the sealing layer, the line width of the straight portion, and the thickness direction at the straight portion. A sealing package C was prepared in the same manner as in Example 1 except that the cross-sectional area of the film and the sealing ratio of the straight portion were changed. The thermal expansion coefficients α ₁ and α _{2 of} the glass material used for sealing and the glass substrate used in Table 1, and the production conditions, the pre-fired layer, the film thickness of the sealing layer, the line width of the linear portion, and the thickness direction of the linear portion The cross-sectional area and the seal ratio of the straight part are shown.

(Example 4)
The pattern line width of the screen mask is 300 μm, the screen printing conditions are adjusted, the film thickness and line width of the pre-fired layer are adjusted as shown in Table 1, and the laser output is further adjusted to adjust the film thickness of the sealing layer. A sealing package D was produced in the same manner as in Example 1 except that the line width of the straight line part, the cross-sectional area in the thickness direction of the straight line part, and the sealing ratio of the straight line part were changed. The thermal expansion coefficients α ₁ and α _{2 of} the glass material used for sealing and the glass substrate used in Table 1, and the production conditions, the pre-fired layer, the film thickness of the sealing layer, the line width of the linear portion, and the thickness direction of the linear portion The cross-sectional area and the seal ratio of the straight part are shown.

(Example 5)
The screen mask pattern line width is 350 μm, and the screen printing conditions are adjusted to adjust the film thickness and line width of the pre-fired layer as shown in Table 1, and the laser output is adjusted to adjust the film thickness of the sealing layer. A sealing package E was produced in the same manner as in Example 1 except that the line width of the straight part, the cross-sectional area in the thickness direction of the straight part, and the sealing ratio of the straight part were changed. The thermal expansion coefficients α ₁ and α _{2 of} the glass material used for sealing and the glass substrate used in Table 1, and the production conditions, the pre-fired layer, the film thickness of the sealing layer, the line width of the linear portion, and the thickness direction of the linear portion The cross-sectional area and the seal ratio of the straight part are shown.

(Example 6)
The same bismuth glass frit, low expansion filler and laser absorber as in Example 1 were used, and the ratio was 63.7 vol% bismuth glass frit, 25.3 vol% cordierite powder, and 11.0 vol laser absorber. percent, and the thermal expansion coefficient alpha ₁ of the sealing glass material and 74 × ^{10 -7} / ℃. Furthermore, as shown in Table 1, the laser output was adjusted to change the film thickness of the sealing layer, the line width of the straight line part, the cross-sectional area in the thickness direction of the straight line part, and the seal ratio of the straight line part. In the same manner as above, sealing packages F were produced. The thermal expansion coefficients α ₁ and α _{2 of} the glass material used for sealing and the glass substrate used in Table 1, and the production conditions, the pre-fired layer, the film thickness of the sealing layer, the line width of the linear portion, and the thickness direction of the linear portion The cross-sectional area and the seal ratio of the straight part are shown.

(Example 7)
The same bismuth glass frit, low expansion filler and laser absorber as in Example 1 were used, and the ratio was 74.4% by volume of bismuth glass frit, 14.9% by volume of cordierite powder and 10.7% of laser absorber. %, The thermal expansion coefficient α ₁ of the sealing glass material was set to 85 × 10 ⁻⁷ / ° C. Furthermore, as shown in Table 1, the laser output was adjusted to change the film thickness of the sealing layer, the line width of the straight line part, the cross-sectional area in the thickness direction of the straight line part, and the seal ratio of the straight line part. A sealing package G was produced in the same manner as described above. The thermal expansion coefficients α ₁ and α _{2 of} the glass material used for sealing and the glass substrate used in Table 1, and the production conditions, the pre-fired layer, the film thickness of the sealing layer, the line width of the linear portion, and the thickness direction of the linear portion The cross-sectional area and the seal ratio of the straight part are shown.
In addition, in the sealing packages A to G of Examples 1 to 7, the line width of the sealing layer is 150 μm or more and less than 450 μm in any part of the linear portion, and the cross-sectional area in the thickness direction is 800 μm ² or more and 2000 μm ^2. The sealing ratio was 100% or more and less than 150%.

(Examples 8 to 10)
In Examples 8 and 9, the pattern line width of the screen mask was 500 μm, in Example 10, the pattern line width of the screen mask was 600 μm, and the screen printing conditions were adjusted, as shown in Table 2, Example 1 except that the line width was adjusted and the laser output was adjusted to change the film thickness of the sealing layer, the line width of the straight part, the cross-sectional area in the thickness direction of the straight part, and the seal ratio of the straight part. Similarly, a sealed package H was produced as Example 8, a sealed package I was produced as Example 9, and a sealed package J was produced as Example 10. The thermal expansion coefficients α ₁ and α _{2 of} the glass material used for sealing and the glass substrate used in Table 2, and the production conditions, the pre-fired layer, the film thickness of the sealing layer, the line width of the linear portion, and the thickness direction of the linear portion The cross-sectional area and the seal ratio of the straight part are shown.

(Example 11)
The thickness of the sealing layer, the line width of the straight portion, the cross-sectional area in the thickness direction of the straight portion, and the seal ratio of the straight portion were changed in the same manner as in Example 1 except that the laser output was adjusted to the low output side. A sealing package K was produced. The thermal expansion coefficients α ₁ and α _{2 of} the glass material used for sealing and the glass substrate used in Table 2, and the production conditions, the pre-fired layer, the film thickness of the sealing layer, the line width of the linear portion, and the thickness direction of the linear portion The cross-sectional area and the seal ratio of the straight part are shown.

[Evaluation]
About the sealing package AK obtained in the said Examples 1-11, the bending strength test was done with the following method and bending strength was evaluated.

(Bending strength test)
As shown in the schematic cross-sectional view in FIG. 4, a four-point bending test jig is prepared, the sealing package obtained above is installed in the center, and the distance between the lower fulcrums is 70 mm and the distance between the upper fulcrums is 35 mm. , Model No .: The load at the time of breakage was measured using TCM1000CR. From these values, the four-point bending strength σ _b4 (MPa) was calculated using the following formula (2).

上記式（２）において、Ｐは、破壊時の荷重［Ｎ］、Ｌ（ラージエル）は、下側支点間の距離［ｍｍ］、ｌ（スモールエル）は、上側支点間の距離［ｍｍ］、ｗは試料の幅［ｍｍ］、ｔは試料の厚み［ｍｍ］である。

In the above formula (2), P is the load at break [N], L (Large L) is the distance between the lower fulcrums [mm], l (Small L) is the distance between the upper fulcrums [mm], w is the width [mm] of the sample, and t is the thickness [mm] of the sample.

  The results are shown in Table 1 for Examples 1 to 7 and in Table 2 for Examples 8 to 11. In addition, when the origin of the crack of the broken sealing package was analyzed with an optical microscope, Examples 1 to 10 were broken from the second glass substrate in the vicinity of the sealing layer. Such a state of fracture is shown as “stress” in the fracture mode column of Tables 1 and 2. On the other hand, Example 11 was destroyed from the interface between the sealing layer and the first glass substrate. Such a state of destruction is shown as “sealing layer” in the destruction mode column of Tables 1 and 2.

  As is clear from Tables 1 and 2, the sealing packages of Examples 1 to 7 are all within the scope of the present invention in terms of the line width, the cross-sectional area in the thickness direction, and the sealing ratio in the straight part of the sealing layer. Therefore, it has excellent 4-point bending strength. On the other hand, the sealing packages of Examples 8 to 11 are sufficient because at least one of the line width, the cross-sectional area in the thickness direction, and the sealing ratio in the straight portion of the sealing layer is outside the scope of the present invention. Does not have point bending strength.

  DESCRIPTION OF SYMBOLS 1 ... Sealing package, 2 ... 1st glass substrate, 2a ... Surface, 3 ... 2nd glass substrate, 3a ... Surface, 4 ... Electronic element part, 5 ... Sealing area | region, 6 ... Sealing layer, 7 ... Temporary fired layer, 10... Laser light.

Claims (5)

A pair of glass substrates facing each other;
A frame shape mainly consisting of a straight portion, and a sealing layer having a thickness of 10 μm or less, disposed so as to seal the vicinity of the outer periphery between the pair of glass substrates;
A sealing region surrounded by inner surfaces of the glass substrate and the sealing layer, and
A sealing package comprising:
The sealing layer is a layer obtained by pre-baking a sealing material layer comprising a sealing glass and a laser absorber and a sealing material layer composed of a vehicle to obtain a pre-firing layer, followed by laser firing,
The line width of the sealing layer in the linear portion is 150 μm or more and less than 450 μm, the cross-sectional area in the thickness direction is 800 μm ² or more and less than 2000 μm ² , and the ratio of the line width of the sealing layer to the line width of the pre-fired layer Is a sealed package which is 100% or more and less than 150%. The difference (α ₁ -α ₂ ) between the thermal expansion coefficient α ₁ of the glass material for sealing and the thermal expansion coefficient α ₂ of the glass substrate is in the range of 15 to 65 × 10 ⁻⁷ / ° C. ₂ . Sealing package.   The sealing package according to claim 1, wherein the sealing glass is bismuth-based glass.   The sealing package of any one of Claims 1-3 which have an electronic element part arrange | positioned at the said sealing area | region.   The sealed package according to any one of claims 1 to 4, wherein the glass substrate has a rectangular shape and a diagonal line length is 4 inches or more.

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