JP5413562B2 - Sealing material - Google Patents

Sealing material Download PDF

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JP5413562B2
JP5413562B2 JP2008307919A JP2008307919A JP5413562B2 JP 5413562 B2 JP5413562 B2 JP 5413562B2 JP 2008307919 A JP2008307919 A JP 2008307919A JP 2008307919 A JP2008307919 A JP 2008307919A JP 5413562 B2 JP5413562 B2 JP 5413562B2
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powder
sealing material
refractory filler
glass
filler powder
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JP2009155200A (en
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邦彦 加納
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日本電気硝子株式会社
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Description

  The present invention relates to a sealing material, and more particularly to a sealing material suitable for a ceramic package, a plasma display panel (hereinafter referred to as PDP) or an organic EL display.

  Conventionally, glass has been used as a sealing material for ceramic packages and the like. Glass is excellent in chemical durability and heat resistance as compared with a resin-based adhesive, and is suitable for securing airtightness of a ceramic package or the like.

  These glasses are required to have various properties depending on the application, but are required to be usable at least at a temperature that does not deteriorate a member used for a ceramic package or the like. Therefore, as a glass that satisfies the above characteristics, lead borate glass having a low melting point characteristic has been widely used (see Patent Document 1).

  However, in recent years, environmental problems have been pointed out with respect to PbO contained in lead borate glass, and it is desired to replace lead borate glass with glass containing no PbO. In response to such environmental demands, various low-melting-point glasses have been developed as substitutes for lead borate glass. The bismuth-based glass described in Patent Document 2 and the like is expected as an alternative candidate because it has substantially the same characteristics as lead borate glass in various characteristics such as thermal expansion coefficient. In fact, it is still not as good as lead borate glass in terms of thermal stability.

In general, the bismuth glass powder used for the sealing material has a thermal expansion coefficient of about l00 to 120 × 10 −7 / ° C., so that the bismuth glass powder alone is an alumina substrate (thermal expansion coefficient: about 76 × 10 −7 / ° C.) and the like, the thermal expansion coefficients of the two do not match, and a large tensile stress remains in the sealed portion, which causes cracks and cracks. In order to prevent such problems, a sealing material is used in which a low expansion refractory filler powder is added to a bismuth glass powder to match the thermal expansion coefficient of an alumina substrate or the like.

Generally, as the refractory filler powder, crystalline materials such as willemite, cordierite, β-eucryptite, zircon, tin oxide, mullite, alumina, zirconia, and the like are used. Further, the greater the content of the refractory filler powder, the lower the thermal expansion coefficient of the sealing material.
Japanese Unexamined Patent Publication No. Sho 63-315536 JP 2003-095597 A

  As described above, if the content of the refractory filler powder is increased, the thermal expansion coefficient of the sealing material is lowered, but the fluidity of the sealing material is likely to be lowered accordingly. If the fluidity of the sealing material is lowered, it becomes difficult to seal the material to be sealed at a low temperature, and the sealing conditions required for various applications cannot be satisfied. For example, if an IC element is mounted on an IC ceramic package and then the IC ceramic package is sealed at a high temperature, the characteristics of the IC element are likely to be deteriorated, resulting in problems such as a decrease in product yield. Therefore, the sealing material used for this application is required to have a low sealable temperature, for example, 460 ° C. or lower.

  By the way, conventionally, many attempts have been made to improve the glass composition as means for improving the fluidity of the sealing material. However, in reality, almost no attempt has been made to improve the fluidity of the sealing material by improving the refractory filler powder. As described above, since bismuth-based glass has a problem in fluidity, there is a high need to improve the refractory filler powder.

In addition, as the content of Bi 2 O 3 in the bismuth-based glass powder is increased, the fluidity of the bismuth-based glass powder is improved. However, when the content of Bi 2 O 3 is 76% by mass or more, Bi 2 O 3 It becomes difficult to improve the fluidity of the sealing material while maintaining the thermal stability of the bismuth-based glass powder. From such a situation, when the content of Bi 2 O 3 in the bismuth-based glass powder is 76% by mass or more, it is highly necessary to improve the refractory filler powder and increase the fluidity of the sealing material.

Therefore, the present invention increases the Bi 2 O 3 content in the bismuth glass powder and improves the shape of the refractory filler powder in the sealing material containing the bismuth glass powder and the refractory filler powder. Thus, the technical problem is to improve the fluidity of the sealing material and improve the characteristics of the ceramic package and the like.

As a result of diligent efforts, the present inventor, in a sealing material containing a bismuth-based glass powder and a refractory filler powder, has a Bi 2 O 3 content of 76% by mass or more in the bismuth-based glass powder and 1 % CuO. The present inventors have found that the above technical problem can be solved by regulating the mass of the refractory filler powder to a substantially spherical shape while limiting to not less than mass%, and propose the present invention. That is, the sealing material of the present invention is a sealing material containing a bismuth-based glass powder and a refractory filler powder. (1) The bismuth-based glass powder is represented by the following oxide equivalent mass% as a glass composition: Bi 2 O 3 76 to 90%, B 2 O 3 2 to 12%, ZnO 1 to 20%, CuO 1 to 10% contained, substantially no PbO, (2) Inclusion of bismuth glass powder The amount is 35 to 95% by volume, the content of the refractory filler powder is 5 to 65% by volume, and (3) the refractory filler powder is substantially spherical.
The “substantially spherical” as used in the present invention is not limited to a true sphere, and in the refractory filler powder, the value obtained by dividing the shortest diameter passing through the center of gravity of the refractory filler powder by the longest diameter is 0.5 or more, preferably 0.7 or more.

The sealing material of the present invention contains bismuth-based glass powder. Bismuth-based glass has better thermal stability and a lower melting point than other lead-free glasses. In the sealing material of the present invention, the bismuth-based glass contains Bi 2 O 3 76 to 90%, B 2 O 3 2 to 12%, and ZnO 1 to 20% as a glass composition in terms of mass%. In this way, it becomes easy to improve the fluidity of the sealing material while maintaining the thermal stability of the bismuth glass powder. In particular, the sealing material of the present invention contains 1 to 10% by mass of CuO as a glass composition. In this way, the thermal stability can be maintained even if the content of Bi 2 O 3 is 76% by mass or more.

The sealing material of this invention contains 5-65 volume% of refractory filler powders. In this way, the thermal expansion coefficient of the sealing material is an alumina substrate (thermal expansion coefficient: about 76 × 10 −7 / ° C.), high strain point glass (thermal expansion coefficient: about 85 × 10 −7 / ° C.), It can be matched with the thermal expansion coefficient of an alkali-free glass substrate (about 32-38 × 10 −7 / ° C.). Here, it is important that the thermal expansion coefficient of the sealing material is designed to be about 5 to 30 × 10 −7 / ° C. lower than the sealed object. This is because the stress remaining in the sealing portion is set to the compression side to prevent cracks in the sealing portion. If the content of the refractory filler powder is more than 65% by volume, the content of the glass powder as the flux is relatively reduced, and the fluidity of the sealing material is likely to be lowered.

  Conventionally, the refractory filler powder has been produced by firing a predetermined oxide raw material and then mechanically grinding it with a ball mill or the like. When the refractory filler powder is mechanically pulverized, it becomes a fractured shape. When the refractory filler powder having a fracture shape is used, a part of the refractory filler powder is easily exposed on the outer surface of the glaze film, and surface protrusions are likely to be formed on the fired film. Inappropriate stress is likely to remain in the vicinity of the surface protrusions. Further, if an object to be sealed is brought into contact with the glaze film, the stress is applied to the object to be sealed, and airtightness of the ceramic package or the like cannot be ensured.

  On the other hand, the sealing material of the present invention regulates the shape of the refractory filler powder to be substantially spherical. In this way, when the bismuth-based glass powder is softened, the fluidity of the bismuth-based glass powder is not easily inhibited by the refractory filler powder, and as a result, the fluidity of the sealing material is improved. Moreover, when the shape of the refractory filler powder is substantially spherical, it becomes easy to obtain a smooth glaze layer. Furthermore, if the shape of the refractory filler powder is substantially spherical, even if a part of the refractory filler powder is exposed on the surface of the glaze layer, the stress of the refractory filler powder is substantially spherical, so the stress in this part is Even if the object to be sealed is dispersed and brought into contact with the glaze layer, undue stress is hardly applied to the object to be sealed, and as a result, airtightness of the ceramic package or the like is easily secured.

  Methods for obtaining a substantially spherical refractory filler powder include methods such as (1) melting method, (2) granulation method, and (3) crystallized glass method. (1) The melting method is a method in which a finely pulverized material of a refractory filler powder is passed through a high-temperature atmosphere, thereby spheroidizing the refractory filler powder with surface tension and then rapidly cooling to obtain a refractory filler powder. It is. (2) The granulation method is a method of obtaining a refractory filler powder by granulating the raw material of the refractory filler powder that has been pre-fired into a substantially spherical shape, followed by firing. (3) The crystallized glass method is a method in which a crystalline glass powder is used as a raw material, an ultrafine powder crystal is added to the raw material, and then fired, and the obtained fired product is crushed to obtain a refractory filler powder. It is.

  Of the methods (1) to (3), (3) the crystallized glass method is the most preferable method for obtaining a substantially spherical refractory filler powder. In the crystallized glass method, since crystalline glass powder is used as a raw material, a homogeneous refractory filler powder can be obtained, and a refractory filler powder can be obtained by short-time firing. Further, the crystallized glass method has an advantage that the pulverization step and the classification step can be simplified because the fired filler powder having a predetermined particle size can be obtained by crushing the obtained fired product.

FIG. 1 is an electron micrograph showing a raw material of a refractory filler powder (cordierite) according to the present invention. In a crystalline glass powder having a cordierite composition, an ultrafine powder Al 2 O 3 has been added. FIG. 2 is an electron micrograph showing the refractory filler powder according to the present invention, and shows the refractory filler powder obtained by firing the raw material of FIG. As is apparent from FIGS. 1 and 2, when the raw material of FIG. 1 is fired, a substantially spherical refractory filler powder can be obtained.

Secondly, the sealing material of the present invention is a sealing material containing a bismuth-based glass powder and a refractory filler powder. (1) The bismuth-based glass powder is expressed as a mass% in terms of the following oxide as a glass composition. And Bi 2 O 3 76 to 90%, B 2 O 3 2 to 12%, ZnO 1 to 20%, CuO 1 to 10%, Fe 2 O 3 0.01 to 3%, and substantially containing PbO. does not contain, (2) bismuth content of the glass powder is 35 to 95 vol%, the content of the refractory filler powder is 5 to 65% by volume, (3) the refractory filler powder is substantially spherical It is characterized by. In this way, it becomes easy to improve the fluidity of the sealing material while maintaining the thermal stability of the bismuth glass powder. In particular, the sealing material of the present invention contains 0.01 to 3% by mass of Fe 2 O 3 as a glass composition. In this way, the thermal stability can be maintained even if the content of Bi 2 O 3 is 76% by mass or more. CuO and Fe 2 O 3 have an effect of suppressing devitrification of the glass at the time of melting or firing, and when both are contained as essential components, the thermal stability can be remarkably improved.

  Thirdly, the sealing material of the present invention is characterized in that the content of the refractory filler powder is 5 to 50% by volume.

Fourth, the sealing material of the present invention is characterized in that the density of the bismuth-based glass powder is 6.0 g / cm 3 or more and the density of the refractory filler powder is 3.0 g / cm 3 or less. To do. Here, “density” in the present invention refers to a value measured by a known Archimedes method.

When the density of the bismuth-based glass powder is 3.0 g / cm 3 or more higher than the density of the refractory filler powder, the refractory filler powder hardly sinks during firing, and a part of the refractory filler powder is easily exposed on the glaze film. Therefore, surface protrusions are likely to occur on the glaze film. However, since the sealing material of the present invention has a substantially spherical shape of the refractory filler powder, even if the density of the bismuth-based glass powder is 3.0 g / cm 3 or more higher than the density of the refractory filler powder. Part of the refractory filler powder is hardly exposed on the glaze film. Moreover, even if a part of the refractory filler powder is exposed on the surface of the glaze film, the refractory filler powder is almost spherical, so the stress in this part is dispersed, and further, the object to be sealed is applied during firing. Even if it comes into contact, it is difficult to apply an undue stress to the object to be sealed, and as a result, it becomes easy to ensure airtightness of the ceramic package or the like.

  Fifth, the sealing material of the present invention is characterized in that the refractory filler powder is cordierite.

Sixth, the sealing material of the present invention has an average particle diameter D 50 of the refractory filler powder is characterized by a 0.5~35Myuemu. Here, the “average particle diameter D 50 ” referred to in the present invention refers to a value measured by a laser diffraction method.

Seventh, the sealing material of the present invention further contains one or more selected from the group of SiO 2 , Al 2 O 3 , ZrO 2 , and TiO 2 as crystal powder, and the crystal powder the average primary particle diameter D 50 of the is characterized in that a 1 to 100 nm. Here, “average primary particle diameter D 50 of crystal powder” refers to a value measured by a laser diffraction method. When preparing a refractory filler powder by the crystallized glass method, if the above-mentioned crystal powder of ultrafine powder is added to the crystalline glass powder, the crystalline glass powder becomes substantially spherical due to surface tension during firing of the refractory filler. Cheap. In addition, SiO 2 , Al 2 O 3 , ZrO 2 and TiO 2 have a primary particle size of ultrafine powder when these chlorides are hydrolyzed in a hydrogen flame, and obtain the above-described highly pure crystal powder. be able to.

  Eighth, the sealing material of the present invention is characterized in that the content of crystal powder is 0.03 to 3% by volume.

  Ninthly, the sealing material of the present invention is characterized by containing substantially no PbO. Here, “substantially not containing PbO” in the present invention refers to the case where the content of PbO in the sealing material is 1000 ppm (mass) or less.

  Tenth, the sealing material of the present invention is used for sealing ceramic packages.

  Tenth, the sealing material of the present invention is used for sealing an organic EL display.

  In the sealing material of the present invention, the mixing ratio of the bismuth-based glass powder and the refractory filler powder is 35 to 95% by volume of the bismuth-based glass powder, 5 to 65% by volume of the refractory filler powder, and the bismuth-based glass powder 50 to 50%. 95% by volume, 5-50% by volume of refractory filler powder is preferable, 60-80% by volume of bismuth-based glass powder, and 20-40% by volume of refractory filler powder are more preferable. When the refractory filler powder is less than 5% by volume, it becomes difficult to enjoy the effect of the refractory filler powder (particularly, the expansion of the sealing material). Since the content of the glass powder is reduced, the fluidity of the sealing material is lowered, and it becomes difficult to seal the ceramic package or the like at a low temperature.

  In the sealing material of the present invention, the value obtained by dividing the shortest diameter passing through the center of gravity of the refractory filler powder by the longest diameter is 0.5 or more, 0.6 or more, 0.7 or more, particularly 0.75 or more. preferable. When the value obtained by dividing the shortest diameter of the refractory filler powder by the longest diameter is less than 0.5, the fluidity of the bismuth glass powder is inhibited by the refractory filler powder when the bismuth glass powder softens. As a result, the fluidity of the sealing material becomes poor. Further, when the value obtained by dividing the shortest diameter of the refractory filler powder by the longest diameter is less than 0.5, it becomes difficult to obtain a smooth glaze film, and a part of the refractory filler powder is formed on the surface of the glaze film. When exposed, stress tends to concentrate on this part, and when sealing, when the sealing object comes into contact with the glaze film, undue stress is likely to be applied to the sealing object, resulting in airtightness of ceramic packages, etc. It becomes difficult to secure.

The bismuth-based glass powder has a lower softening point and a higher density as the Bi 2 O 3 content in the glass composition increases. That is, as the fluidity of the bismuth-based glass powder is increased, the density of the bismuth-based glass increases, and the density difference between the bismuth-based glass powder and the refractory filler powder increases. On the other hand, when the density difference between the bismuth glass powder and the refractory filler powder increases, a part of the refractory filler powder is easily exposed on the outer surface of the glaze film. However, since the sealing material of the present invention has a substantially spherical shape of the refractory filler powder, such a situation hardly occurs and the degree of freedom in material design can be increased. In particular, when the Bi 2 O 3 content in the bismuth-based glass powder is 76% by mass or more, the fluidity of the sealing material is improved, but the density tends to be 6.0 g / cm 3 or more. Cordierite has a low coefficient of thermal expansion but a density of 3.0 g / cm 3 or less. From such a viewpoint, in the sealing material of the present invention, the density of the bismuth-based glass powder is preferably 6.0 g / cm 3 or more and / or the density of the refractory filler powder is preferably 3.0 g / cm 3 or less. More preferably, the density of the glass-based glass powder is 6.8 g / cm 3 or more and / or the density of the refractory filler powder is 2.9 g / cm 3 or less, and the density of the bismuth-based glass powder is 7.0 g / cm 3 or more and / or Alternatively, the density of the refractory filler powder is more preferably 2.7 g / cm 3 or less. Further, in the sealing material of the present invention, the density of the bismuth-based glass powder is 3.0 g / cm 3 or more, 3.7 g / cm 3 or more, particularly 4.3 g / cm 3 or more than the density of the refractory filler powder. Larger is preferred.

In the sealing material of the present invention, the average particle diameter D50 of the refractory filler powder is preferably 0.5 to 35 μm, 1 to 25 μm, 5 to 20 μm, particularly preferably 7 to 15 μm. When the average particle diameter D 50 of the refractory filler powder is smaller than 0.5 μm, the refractory filler powder is easily dissolved in the bismuth glass powder during firing, and the compatibility between the bismuth glass powder and the refractory filler powder is low. In addition, the thermal stability of the sealing material tends to be lowered. Further, the average particle diameter D 50 of the refractory filler powder is 0.5μm less, dissolution of the refractory filler powder becomes excessive at the time of firing, the softening point of the sealing material increases unduly, sealing at a low temperature It becomes difficult to do. On the other hand, the average and particle size D 50 is greater than 35μm of refractory filler powder, only the proportion of coarse components of the refractory filler powder is increased relatively, the micro cracks are likely to occur in sealing part, a ceramic package Airtight defects are likely to occur. The average and particle size D 50 is greater than 35μm of refractory filler powder, if the average particle diameter D 50 of the bismuth-based glass powder is small, that is difficult to uniformly mix the bismuth-based glass powder and the refractory filler powder In addition, when the sealing material is a paste material, the bismuth-based glass powder and the refractory filler powder are easily separated, and the life of the paste material (so-called pot life) is shortened.

  In the sealing material of the present invention, cordierite, willemite, zircon, zirconium phosphate, β-quartz solid solution, zinc petalite, β-eucryptite, garnite and the like are suitable as the refractory filler powder. Since these refractory filler powders have a low coefficient of thermal expansion, the coefficient of thermal expansion of the sealing material can be reduced. In particular, cordierite powder has a low coefficient of thermal expansion, good compatibility with bismuth glass, and hardly impairs the thermal stability of the sealing material.

  In the sealing material of the present invention, in addition to the substantially spherical refractory filler powder, other shapes of refractory filler powder, such as other shapes, within a range that does not impair the effects of the present invention (for example, 10% by volume or less). Willemite, zircon, tin oxide, zirconia, alumina, cordierite, niobium oxide, β-eucryptite, titanium oxide, silica, garnite, quartz glass and the like may be added.

In the sealing material of the present invention, the bismuth-based glass powder has a glass composition represented by mass% in terms of the following oxide, Bi 2 O 3 76 to 90%, B 2 O 3 2 to 12%, ZnO 1 to 20 %, CuO 1 to 10% is preferable. The reason for limiting the glass composition range of the bismuth-based glass powder as described above will be described below.

Bi 2 O 3 is a main component for lowering the softening point. The content is 76 to 90%, preferably 76 to 89%, more preferably 78 to 87%, and still more preferably 80 to 85%. If the content of Bi 2 O 3 is less than 76%, the softening point becomes too high, and sealing becomes difficult at a low temperature of 460 ° C. or lower. On the other hand, when the content of Bi 2 O 3 is more than 90%, the glass becomes thermally unstable, and the glass tends to devitrify during melting or firing.

B 2 O 3 is a component that forms a glass network of bismuth-based glass and is an essential component. Its content is 2 to 12%, preferably 3 to 10%, more preferably 4 to 10%, still more preferably 5 to 9%. If the content of B 2 O 3 is less than 2%, the glass becomes thermally unstable, and the glass tends to devitrify during melting or firing. On the other hand, if the content of B 2 O 3 is more than 12%, the viscosity of the glass becomes too high, and low-temperature sealing at 460 ° C. or lower becomes difficult.

  ZnO is a component that suppresses the devitrification of the glass during melting or firing, and the content thereof is 1 to 20%, preferably 3 to 15%, more preferably 4 to 12%, still more preferably 5 to 10%. Is less than. When the ZnO content is less than 1%, it is difficult to obtain an effect of suppressing devitrification of the glass at the time of melting or firing. When the content of ZnO is more than 20%, the component balance of the glass composition is impaired, and conversely, the thermal stability is lowered, and as a result, the glass is easily devitrified.

CuO and Fe 2 O 3 have an effect of suppressing devitrification of the glass at the time of melting or firing, and particularly when CuO is contained as an essential component, the thermal stability can be remarkably improved. CuO is a component to suppress the devitrification of the glass during melting or during sintering, the content of 1 10%, 1-5% especially preferred. When the content of CuO is more than 10%, the component balance of the glass composition is impaired, and conversely, the thermal stability is lowered, and as a result, the glass is easily devitrified. Further, from the viewpoint of improving thermal stability, it is preferable to add CuO as an essential component, and specifically, the content of CuO is preferably set to 1 % or more. Fe 2 O 3 has the same effect as CuO and has the effect of suppressing devitrification of the glass during melting or firing, and its content is 0 to 3%, preferably 0 to 1.5%. . When the content of Fe 2 O 3 is more than 3%, is impaired balance of components glass composition, thermal stability is lowered conversely, as a result, the glass tends to be devitrified. Further, from the viewpoint of improving thermal stability, it is preferable to add Fe 2 O 3 as an essential component, and specifically, the content of Fe 2 O 3 is preferably 0.01% or more.

  In addition to the above components, for example, the following components can be added up to 20% in the glass composition.

Al 2 O 3 is a component that improves weather resistance, and its content is 0 to 5%, preferably 0 to 2%. When the content of Al 2 O 3 is more than 5%, too high softening point, it is difficult to cold sealing of 460 ° C. or less.

SiO 2 is a component for improving the weather resistance, the content thereof is 0-10%, preferably 0-3%, more preferably less than 0 to 1%. When the content of SiO 2 is more than 10%, the softening point becomes too high, and low-temperature sealing at 460 ° C. or less becomes difficult.

  BaO, SrO, MgO, and CaO are components having an effect of suppressing devitrification of the glass at the time of melting or firing, and these components can be added to the glass composition up to 15% in total. When the total amount of these components is more than 15%, the softening point becomes too high, and low-temperature sealing at 460 ° C. or less becomes difficult.

  The BaO content is preferably 0 to 10%, 0 to 8%, and more preferably 1 to 5%. When there is more content of BaO than 10%, the component balance of a glass composition will be impaired, conversely, thermal stability will fall and as a result, glass will become easy to devitrify. Further, from the viewpoint of improving the thermal stability, it is preferable to add BaO as an essential component, and specifically, the content of BaO is preferably set to 1% or more.

  Each content of SrO, MgO, and CaO is preferably 0 to 5%, particularly preferably 0 to 2%. When the content of each component is more than 5%, the glass is easily devitrified or phase-separated.

CeO 2 is a component that suppresses devitrification of the glass at the time of melting or firing, and its content is 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%. When the content of CeO 2 is more than 5%, the component balance of the glass composition is impaired, and conversely, the thermal stability is lowered. As a result, the glass is easily devitrified, and the fluidity is easily lowered. . Further, from the viewpoint of improving the thermal stability, it is preferable to add a small amount of CeO 2 , and specifically, the content of CeO 2 is preferably 0.01% or more.

Sb 2 O 3 is a component for suppressing devitrification of the glass, and its content is 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%. Sb 2 O 3 has an effect of stabilizing the network structure of the bismuth-based glass. If Sb 2 O 3 is appropriately added to the bismuth-based glass, even if the content of Bi 2 O 3 is 76% or more. , Thermal stability is difficult to decrease. However, if the content of Sb 2 O 3 is more than 5%, the component balance of the glass composition is impaired, and conversely, the thermal stability is lowered. As a result, the glass is easily devitrified, and the fluidity is low. It tends to decrease. Further, from the viewpoint of improving the thermal stability, it is preferable to add a small amount of Sb 2 O 3 , and specifically, the content of Sb 2 O 3 is preferably 0.05% or more.

WO 3 is a component for suppressing devitrification of the glass, and its content is preferably 0 to 10%, more preferably 0 to 2%. When the content of WO 3 is more than 10%, the component balance of the glass composition is impaired, and conversely, the thermal stability is lowered, and as a result, the glass is easily devitrified.

In 2 O 3 and Ga 2 O 3 are components for suppressing devitrification of the glass, and their content is preferably 0 to 5%, more preferably 0 to 3% in total. If the content of In 2 O 3 and Ga 2 O 3 is more than 5% in total, the component balance of the glass composition is impaired, conversely, the thermal stability is lowered, and as a result, the glass is devitrified. It becomes easy. In addition, the content of In 2 O 3 is preferably 0 to 1%, and the content of Ga 2 O 3 is preferably 0 to 0.5%.

  The oxides of Li, Na, K, and Cs are components that lower the softening point. However, since they have an action of promoting devitrification of the glass at the time of melting, the total content is 2% or less. preferable.

P 2 O 5 is a component that suppresses the devitrification of the glass at the time of melting. If the content is more than 1%, the glass is likely to phase-separate at the time of melting.

MoO 3 , La 2 O 3 , Y 2 O 3 and Gd 2 O 3 are components that suppress the phase separation of the glass at the time of melting, but if the total amount of these is more than 3%, the softening point becomes too high. Low temperature sealing at 460 ° C. or lower becomes difficult.

  Moreover, even if it is another component, it can add to a glass composition to 10% (preferably 5%) in the range which does not impair the characteristic of glass.

The bismuth-based glass powder having the above glass composition exhibits good fluidity at a low temperature and has a thermal expansion coefficient of about 100 to 120 × 10 −7 / ° C. in a temperature range of 30 to 250 ° C.

Sealing material of the present invention as described above, it is preferred not to substantially contain PbO environmental reasons. Moreover, when PbO is contained in the glass composition, Pb 2+ present in the glass diffuses, and the electrical insulation of the sealing material may be lowered.

The sealing material of the present invention preferably further contains crystal powder, and more preferably one or more selected from the group of SiO 2 , Al 2 O 3 , ZrO 2 , and TiO 2 . SiO 2 , Al 2 O 3 , ZrO 2 and TiO 2 are preferable because they have a high melting point equal to or higher than that of the refractory filler powder and can be easily processed into an ultrafine powder. In particular, when the refractory filler powder is cordierite, Al 2 O 3 is suitable because it has the property of hardly reacting with the raw crystalline glass powder.

In the sealing material of the present invention, the average primary particle diameter D50 of the crystal powder is preferably 1 to 100 nm, 5 to 50 nm, and particularly preferably 7 to 40 nm. The average primary particle diameter D 50 of the crystal powder is 1nm less, during the firing of the refractory filler, crystalline powder is easily dissolved in the crystalline glass powder, it becomes difficult to exhibit the desired effect. On the other hand, the average primary particle diameter D 50 of the crystalline powder is greater than 100 nm, it becomes difficult to uniformly coat the crystalline glass powder, during firing of the refractory filler, crystalline glass powder particles tends to firmly sinter.

BET specific surface area of the crystal powder is preferably 10~500m 2 / g, 50~380m 2 / g is more preferable. When the BET specific surface area of the crystal powder is smaller than 10 m 2 / g, it becomes difficult to uniformly coat the crystalline glass powder, and the crystalline glass powders are easily sintered firmly when the refractory filler is fired. When the BET specific surface area of the crystal powder is larger than 500 m 2 / g, the crystal powder is easily dissolved in the crystalline glass powder at the time of firing the refractory filler, and the desired effect is hardly exhibited.

  In the sealing material of the present invention, the content of the crystal powder is preferably 0.03 to 3% by volume, more preferably 0.05 to 1% by volume. When the content of the crystalline powder is less than 0.03% by volume, it becomes difficult to uniformly coat the crystalline glass powder during firing of the refractory filler, and the crystalline glass powder is hardly sintered, so that the refractory filler powder However, the fluidity of the sealing material tends to be reduced. Moreover, when there is less content of crystal powder than 0.03 volume%, the crushing time of a refractory filler will become unduly long, and the preparation efficiency of a refractory filler powder will fall. On the other hand, if the content of the crystal powder is more than 3% by volume, the crystal powder becomes excessive, and when the sealing material is baked, the excess crystal powder is dissolved in the bismuth glass, and the fluidity of the sealing material is low. There is a risk of damage.

  The sealing material of the present invention is preferably used for sealing a ceramic package. The ceramic package uses a member having low heat resistance, such as an IC element or a conductive adhesive, and therefore needs to be sealed at a low temperature. Since the sealing material of the present invention can be sealed at a low temperature, it is suitable for this application. In addition, when the fluidity of the sealing material is low, the refractory filler powder is likely to be exposed on the outer surface of the glaze layer, and undue stress is likely to remain in the exposed portion, so that cracks are likely to occur in the ceramic package. Become. However, since the sealing material of this invention is excellent in fluidity | liquidity, such a situation can be avoided effectively. Furthermore, since the sealing material of the present invention has a substantially spherical shape, even if the refractory filler powder is exposed to the sealing layer, the stress concentration in the exposed portion can be alleviated, and the ceramic package has cracks. The situation that occurs can be effectively avoided.

  The sealing material of the present invention is particularly preferably used for sealing an IC ceramic package or a crystal resonator ceramic package. When the IC ceramic package is sealed at a temperature exceeding 460 ° C., the IC element is deteriorated. However, the sealing material of the present invention can be satisfactorily sealed at a temperature of 460 ° C. or less, and thus is suitable for this application. . Further, when the quartz resonator ceramic package is sealed at a temperature exceeding 460 ° C., the conductive adhesive deteriorates and the element is deteriorated. However, the sealing material of the present invention is well sealed at a temperature of 460 ° C. or lower. Since it can be worn, it is suitable for this application.

  The sealing material of the present invention is preferably used for sealing a flat display device. Since the flat display device uses a member having low heat resistance, for example, a phosphor, the necessity for sealing at a low temperature is high. Since the sealing material of the present invention can be sealed at a low temperature, it is suitable for this application.

  In the PDP manufacturing process, the sealing material undergoes the following baking process. First, the sealing material dispersed in the vehicle is applied to the outer peripheral edge of the rear glass substrate of the PDP, and primary firing (glazing process, pre-baking process) is performed, and the vehicle components are pyrolyzed or incinerated at a high temperature. The primary firing step is performed under a temperature condition where the resin used in the vehicle is completely thermally decomposed, for example, about 400 to 500 ° C. Next, the front glass substrate and the rear glass substrate of the PDP are sealed by secondary firing (sealing process, sealing process). The secondary firing step is performed under a temperature condition where the sealing material is softened and deformed, for example, about 450 to 500 ° C. Finally, the inside of the PDP is evacuated through the exhaust pipe, and then a necessary amount of rare gas is injected to seal the exhaust pipe. Since the sealing material of this invention is excellent in fluidity | liquidity and excellent in thermal stability, it can be used conveniently at the said process. Further, when the fluidity of the sealing material is low, the refractory filler powder is likely to be exposed on the outer surface of the glaze layer after the primary firing, and if the front glass substrate is brought into contact with this exposed portion, Cracks are likely to occur at the contact part. However, since the sealing material of this invention is excellent in fluidity | liquidity, such a situation can be avoided effectively. Furthermore, even if the refractory filler powder is exposed to the glaze layer after the primary firing, since the shape is substantially spherical, the stress concentration in the exposed portion can be alleviated, and cracks occur in the flat display device. It can be effectively avoided.

  The sealing material of the present invention is preferably used for an organic EL display. In this way, airtightness in the organic EL display can be ensured, and as a result, deterioration of the organic light emitting layer and the like over time can be prevented, and the life of the organic EL display can be extended.

The organic EL display needs to be sealed at a low temperature because the organic light emitting layer, TFT, and the like are likely to be thermally deteriorated. Under such circumstances, in the technical field of organic EL displays, in order to suppress thermal deterioration of the constituent members, studies have been made to locally heat the sealing material with laser light or the like and seal the glass substrates together. In the sealing material of the present invention, if CuO is added in an amount of 1 % or more in the glass composition, the bismuth-based glass can easily absorb laser light or the like and can be used for this application. Furthermore, in the sealing material of the present invention, if Fe 2 O 3 is added to the glass composition in an amount of 0.01% or more, 0.1% or more, particularly 0.5% or more, the bismuth-based glass further emits laser light or the like. It becomes easy to absorb and can be suitably used for this application. Moreover, since the sealing material of this invention flows favorably in a low temperature range, it can seal glass substrates firmly by local heating, such as a laser beam.

When used for sealing an organic EL display, the thermal expansion coefficient of the sealing material is preferably less than 60 × 10 −7 / ° C., and more preferably less than 52 × 10 −7 / ° C. Generally, an alkali-free glass substrate (40 × 10 −7 / ° C. or less) is used for the organic EL display. If the thermal expansion coefficient of the sealing material is restricted to less than 60 × 10 −7 / ° C., even if an alkali-free glass substrate is used, it becomes difficult for undue tensile stress to remain in the sealed portion, which is caused by a difference in expansion. Cracks are less likely to occur. In addition, if content of a refractory filler powder shall be 50-65 volume%, it will become easy to make the thermal expansion coefficient of a sealing material less than 52 * 10 < -7 > / degreeC .

  Since the bismuth-based glass powder of the present invention has good devitrification resistance and good resistance to iodine electrolyte, it is a sealing material for dye-sensitized solar cells, a coating material for current collecting electrodes, and a partition wall forming material Etc. are also suitable.

In the sealing material of the present invention, the refractory filler powder is preferably produced by the above-described (3) crystallized glass method. In the crystallized glass method, it is preferable to add crystal powder when preparing the raw material of the refractory filler powder, preferably when pulverizing the raw crystal glass to obtain the crystal glass powder. When the crystalline glass is pulverized when the crystalline glass is pulverized, the crystalline glass powder and the crystalline powder can be uniformly mixed in addition to omitting the mixing step of the crystalline glass powder and the crystalline powder. In addition, in the crystallized glass method, when producing a refractory filler powder, in order to increase the meltability of the crystalline glass as a raw material, the glass composition of the crystalline glass includes components other than the crystalline constituents of the refractory filler powder. For example, B 2 O 3 , R 2 O (R 2 O indicates Li 2 O, Na 2 O, K 2 O, Cs 2 O), R′O (R′O is MgO, CaO, SrO, It is preferable to add 0.1 to 10% by mass of BaO). When these components are less than 0.1% by mass, it becomes difficult to increase the meltability of the crystalline glass. Even if the glass composition of the crystalline glass powder deviates somewhat from the theoretical composition of the refractory filler powder, desired crystals can be precipitated. However, when these components are more than 10% by mass, it is difficult to precipitate desired crystals. Furthermore, in the crystallized glass method, it is preferable to provide a step of adjusting the particle size distribution of the crystalline glass powder as a raw material, for example, a classification step of the crystalline glass powder, when producing the refractory filler powder. In this way, the particle size distribution of the refractory filler powder can be easily adjusted.

Hereinafter, based on an Example, this invention is demonstrated in detail. Table 1-4, specimen No. 1-20 are shown.

  Each sample described in Tables 1 to 4 was produced as follows.

First, a glass batch prepared by preparing raw materials such as various oxides and carbonates so as to have the glass compositions shown in Tables 1 to 4 was prepared, and this was put in a platinum crucible and melted at 900 to 1100 ° C. for 1 to 2 hours. did. Next, a part of the molten glass was poured out into a stainless steel mold as a push rod type thermal expansion coefficient measurement (TMA) apparatus and a sample for density measurement, and the other molten glass was formed into a flake shape with a water-cooled roller. The TMA and the density measurement sample were subjected to a predetermined slow cooling treatment after molding. Finally, the flaky glass was pulverized with a ball mill and then passed through a sieve having an opening of 45 μm to obtain each bismuth glass powder having an average particle diameter D 50 of about 10 μm.

  The density, thermal expansion coefficient, glass transition point, and softening point were determined for each bismuth-based glass powder. The density was measured by the well-known Archimedes method. The thermal expansion coefficient and glass transition point were measured with a TMA apparatus. The thermal expansion coefficient was measured in the temperature range of 30 to 300 ° C. Furthermore, the softening point was measured with a differential thermal analysis (DTA) apparatus.

  Next, each bismuth glass powder in Tables 1 to 4 and a predetermined refractory filler powder in the table were mixed, and sample No. 1-20 were obtained. Sample No. About 1-20, the flow diameter, devitrification state, surface protrusion, and crack resistance were evaluated.

  As for the flow diameter, a powder having a mass corresponding to the synthesis density of each sample was dry-pressed into a button shape having an outer diameter of 20 mm using a die, and this was pressed into a 40 mm × 40 mm × 2.8 mm thick high strain point glass substrate (Nippon Electric Glass). It was placed on PP-8C), heated in air at a rate of 5 ° C./min, baked at 460 ° C. for 10 minutes, and then cooled to room temperature at 5 ° C./min. Evaluation was made by measuring the diameter of the button. Here, the synthetic density is a theoretical density calculated from the density of glass and the density and volume ratio of the refractory filler. Moreover, if a flow diameter is 19 mm or more, it means that it can seal by baking for 10 minutes at 460 degreeC. Sample No. No. 17 was fired at 480 ° C. for 10 minutes, and the flow diameter was evaluated.

  The devitrification state was evaluated as follows. Sample No. After holding the powder pressure-molded body of 1 to 20 in a firing furnace at 460 ° C. for 10 minutes, the surface crystal of the fired sample is observed using an optical microscope (magnification 100 times), thereby devitrifying the state. evaluated. The case where devitrification was not recognized was indicated as “◯”, and the case where devitrification was observed was indicated as “x”. The temperature raising / lowering speed was 10 ° C./min. Sample No. About 17 and 20, baking was performed also for 480 degreeC for 10 minutes, and the devitrification state was evaluated.

Surface protrusions were evaluated as follows. First, each sample and acrylic resin-containing α-terpineol were uniformly kneaded and processed into a glass paste, and then the edge of a 100 × 100 × 3 mm high strain point glass substrate (Nippon Electric Glass Co., Ltd. PP-8C). The coating was applied linearly (80 × 3 × 3 mm) to the part and dried at 120 ° C. for 15 minutes. Next, after firing this sample, the outer surface of the obtained glaze film was confirmed with an optical microscope. If the outer surface of the glaze film was not partially exposed to the fireproof filler powder, A part of the conductive filler powder that was exposed was evaluated as “x”. Firing was performed in air, the temperature was increased from room temperature at a rate of 5 ° C./min, held at 440 ° C. for 10 minutes, and then decreased to room temperature at 5 ° C./min. Sample No. For No. 17, firing was performed at 460 ° C. for 10 minutes, and surface protrusions were evaluated. Crack resistance was evaluated using a button-like sample subjected to measurement of the flow diameter. Observe the surface of the button-shaped sample and the glass substrate directly under the button with a stereomicroscope (200 ×). “○” indicates that the button surface and the glass substrate are not cracked, and “×” indicates that the button is generated. As evaluated.

Sample No. The refractory filler powders 1 to 15, 17 and 18 were produced by the following method. First, a glass raw material was prepared so as to obtain a predetermined crystal, and after mixing, it was melted at 1400 to 1550 ° C. to obtain a crystalline glass. Next, by pulverizing a crystalline glass obtained, the average particle diameter D 50 was obtained crystallizable glass powder 10 [mu] m. At the time of pulverization of the crystalline glass, it was added crystalline powder in the table (an average primary particle diameter D 50 = 20nm). Subsequently, after baking this sample for 10 hours at 1300 ° C., the obtained fired product was crushed to obtain a refractory filler powder having an average particle diameter D 50 = 10 μm. In the refractory filler powder obtained by this method, the value obtained by dividing the shortest diameter passing through the center of gravity of the refractory filler powder by the longest diameter was 0.7 or more. Sample No. in Table 4 The refractory filler powder described in No. 16 was prepared by first preparing an oxide raw material so that a predetermined refractory filler powder was obtained. Next, the raw material of the refractory filler powder was granulated with a spray dryer so as to be substantially spherical, and then fired at 1400 ° C. for 10 hours to obtain a refractory filler powder having an average particle diameter D 50 of 10 μm. In the refractory filler powder obtained by this method, the value obtained by dividing the shortest diameter passing through the center of gravity of the refractory filler powder by the longest diameter was 0.75 or more.

Sample No. The refractory filler powders 19 and 20 were obtained by the following method. First, an oxide raw material is prepared so that a predetermined refractory filler powder is obtained, and after mixing, calcined at 1400 ° C. for 10 hours, this calcined product is pulverized with a ball mill, and then classified with a 350 mesh sieve. a particle diameter D 50 was obtained refractory filler powder 10 [mu] m. In the refractory filler powder obtained by this method, the value obtained by dividing the shortest diameter passing through the center of gravity of the refractory filler powder by the longest diameter was about 0.3.

  Sample No. 1-16 flowed well at 460 ° C. for 10 minutes, and had low melting point characteristics suitable for sealing ceramic packages and the like. Furthermore, sample no. In Nos. 1 to 16, since the evaluation of the devitrification state, the surface protrusion, and the crack resistance is good, it is considered that the airtightness of the ceramic package or the like can be secured. Sample No. No. 17 had a large content of refractory filler powder. It is considered that the firing temperature needs to be raised more than 1-16.

  Sample No. No. 18 had poor crack resistance because the content of the refractory filler powder was outside the predetermined range. Sample No. In Nos. 19 and 20, since the shape of the refractory filler powder was not substantially spherical, the evaluation of fluidity and surface protrusion was poor.

  The sealing material of the present invention is suitable for a ceramic package such as a quartz crystal ceramic package and an IC ceramic package. In addition, the sealing material of the present invention includes PDP, various types of field emission displays having various electron-emitting devices, organic EL displays, inorganic EL displays, flat display devices such as fluorescent display tubes, dye-sensitized solar cells, etc. Suitable for solar cells.

It is an electron micrograph which shows the raw material of the refractory filler powder (cordierite) which concerns on this invention. It is an electron micrograph which shows the refractory filler powder which concerns on this invention.

Claims (11)

  1. In a sealing material containing bismuth glass powder and refractory filler powder,
    (1) Bismuth-based glass powder as a glass composition in terms of mass% in terms of the following oxide, Bi 2 O 3 76 to 90%, B 2 O 3 2 to 12%, ZnO 1 to 20%, CuO 1 to Containing 10%, substantially free of PbO,
    (2) The content of the bismuth-based glass powder is 35 to 95% by volume, the content of the refractory filler powder is 5 to 65% by volume,
    (3) A sealing material, wherein the refractory filler powder is substantially spherical.
  2. In a sealing material containing bismuth glass powder and refractory filler powder,
    (1) The bismuth-based glass powder has a glass composition in terms of mass% in terms of the following oxides, Bi 2 O 3 76 to 90%, B 2 O 3 2 to 12%, ZnO 1 to 20%, CuO 1 to 10% Fe 2 O 3 and 0.01 to 3% contains substantially no PbO,
    (2) The content of the bismuth-based glass powder is 35 to 95% by volume, the content of the refractory filler powder is 5 to 65% by volume,
    (3) The sealing material according to claim 1, wherein the refractory filler powder is substantially spherical.
  3.   The sealing material according to claim 1 or 2, wherein the content of the refractory filler powder is 5 to 50% by volume.
  4. The density of the bismuth-based glass powder is 6.0 g / cm 3 or more, and the density of the refractory filler powder is 3.0 g / cm 3 or less. Sealing material.
  5.   The sealing material according to any one of claims 1 to 4, wherein the refractory filler powder is cordierite.
  6. Sealing material according to claim 1, the average particle diameter D 50 of the refractory filler powder is characterized by a 0.5~35Myuemu.
  7. Furthermore, the crystal powder contains one or more selected from the group of SiO 2 , Al 2 O 3 , ZrO 2 and TiO 2 , and the average primary particle diameter D 50 of the crystal powder is 1 to 100 nm. The sealing material according to claim 1, wherein the sealing material is provided.
  8. Sealing material according to any one of claims 1 to 7, the content of the crystal powder is characterized in that 0.03 to 3% by volume.
  9. The sealing material according to any one of claims 1 to 8, wherein the refractory filler powder is produced by a crystallized glass method.
    Is preferred.
  10.   The sealing material according to claim 1, wherein the sealing material is used for sealing a ceramic package.
  11. The refractory filler powder is produced by adding a crystalline powder to a crystalline glass powder and then firing, and crushing the obtained fired product. Sealing material.
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JP5458579B2 (en) * 2008-02-28 2014-04-02 日本電気硝子株式会社 Sealing material for organic EL display
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JP5605748B2 (en) * 2010-04-22 2014-10-15 日本電気硝子株式会社 Refractory filler powder, sealing material and method for producing refractory filler powder
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CN102892724B (en) * 2010-05-10 2015-04-01 日本电气硝子株式会社 Fire-resistant filler, sealing material using same, and method for producing fire-resistant filler
WO2011142215A1 (en) * 2010-05-10 2011-11-17 日本電気硝子株式会社 Fire-resistant filler, sealing material using same, and method for producing fire-resistant filler
JP2012012231A (en) 2010-06-29 2012-01-19 Central Glass Co Ltd Lead-free low melting point glass composition
JP5779922B2 (en) * 2011-03-16 2015-09-16 日本電気硝子株式会社 refractory filler and sealing material using the same
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JP6075715B2 (en) * 2012-09-25 2017-02-08 日本電気硝子株式会社 Bismuth glass and sealing material using the same
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