Glass composition

Glass composition {GLASS COMPOSITION}

<p>The present invention relates to a lead-free glass composition that can be used for bonding or the like at low temperatures. </p>

<p>In an image display apparatus that hermetically seals a front plate and a rear plate, such as a plasma display panel (PDP), a glass composition softened at a low temperature is used for hermetic sealing. Conventionally, as such a glass composition, a sealing material in which a filler is mixed with a glass containing lead oxide as a main component has been used.</p><p>In recent years, the use of lead-containing materials has been avoided due to environmental and safety regulations. As a lead-free glass composition for sealing, Japanese Patent Application Laid-Open No. Hei 10-139478 (Patent Document 1) discloses a glass composition containing bismuth oxide as a main component, and Japanese Patent Application Laid-Open No. 7-69672 (Patent Document 2) discloses a glass composition containing bismuth oxide as a main component. A glass composition containing tin oxide as a main component, Japanese Patent Application Laid-Open No. 2004-250276 (Patent Document 3), and Japanese Patent Application Laid-Open No. 2006-342044 (Patent Document 4) have proposed a glass composition containing vanadium oxide as a main component.</p><p>[Patent Document 1]</p><p>Japanese Patent Laid-Open No. 10-139478</p><p>[Patent Document 2]</p><p>Japanese Patent Laid-Open No. 7-69672</p><p>[Patent Document 3]</p><p>Japanese Patent Laid-Open No. 2004-250276</p><p>[Patent Document 4]</p><p>Japanese Patent Laid-Open No. 2006-342044</p>

<solutionproblem><p>Glass containing lead is widely used because it can be softened at a low temperature. Moreover, practical use of the glass containing bismuth is also made|formed as a substitute for the glass containing lead. However, since a large amount of lead is generated in the extraction of bismuth, it is undesirable for the environment and safety like lead. Then, the objective of this invention is providing the glass composition which can be softened at low temperature without using lead or bismuth.</p><p>In addition, when a glass composition containing bismuth is used as a main component for sealing when manufacturing an image display device, the softening temperature is high and high temperature is required for sealing. needs to be avoided. In addition, in a glass composition containing bismuth as a main component, bismuth is easily reduced, so it is reduced by the atmosphere used in manufacturing an image display device, so that the electrical resistance of the sealed portion is likely to change, resulting in product non-uniformity.</p><p>When a glass composition containing tin as a main component is used in a sealing part, it reacts with moisture and deteriorates easily. For example, when a glass containing tin as a main component is used as a sealing glass composition for manufacturing an image display device such as a plasma display, the sealing portion is corroded by moisture generated by sintering of the phosphor material, and the airtightness is easily reduced. . When a glass composition containing vanadium and phosphorus as a main component is brought into contact with a silver wiring or a copper wiring used in a display device, there is a problem in that the wiring corrodes and the resistance value of the wiring increases or bubbles are generated.</p><p>Accordingly, another object of the present invention is to provide a glass composition suitable for sealing an image display device.</p></solutionproblem><meansproblemsolution><p>A feature of the present invention that achieves the above object is a glass substantially free of lead and bismuth and containing vanadium and phosphorus as main components, and has a resistivity of 10 at 25°C.<sp>9</sp>Ωcm or greater in the glass composition. The glass preferably further contains manganese and barium. In addition, it is preferable to contain at least one of alkali metals, antimony, tellurium, zinc, silicon, aluminum, niobium, and rare earth elements.</p><p>Moreover, it is preferable to contain 1 or more types of alkali metal, antimony, tellurium, zinc, silicon, aluminum, niobium, a rare earth element, iron, tungsten, and molybdenum. </p><p>In the present invention, the glass composition includes a glass matrix composed of a glass forming component, and a glass composition containing at least one of a pigment such as a filler and a black pigment, and a metal powder. </p><p>The glass composition described above can be widely used as a sealing material, a glass for wiring formation, and a material for a structural material. Preferred components of the glass composition are vanadium oxide (V) in terms of oxides of each component.<sb>2</sb>O<sb>5</sb>) is 33 to 45% by weight, phosphorus oxide (P<sb>2</sb>O<sb>5</sb>) is 22 to 30% by weight, manganese oxide (MnO) is 5 to 15% by weight, and barium oxide (BaO) is 10 to 20% by weight. Examples of the alkali metal include Li (lithium), Na (sodium), K (potassium), Rb (rubidium), and Cs (cesium), R<sb>2</sb>It is preferable to contain 0 to 8% by weight in terms of O (R is an alkali metal element). Also, Sb<sb>2</sb>O<sb>3</sb>, TeO<sb>2</sb>, ZnO, SiO<sb>2</sb>, Al<sb>2</sb>O<sb>3</sb>, Nb<sb>2</sb>O<sb>5</sb>, La<sb>2</sb>O<sb>3</sb>(La is a rare earth element) is preferably contained in an amount of 0 to 10% by weight in total.</p><p>In addition, preferred components of the glass composition are vanadium oxide (V) in terms of oxides of each component.<sb>2</sb>O<sb>5</sb>) is 30 to 45% by weight, phosphorus oxide (P<sb>2</sb>O<sb>5</sb>) is 22 to 30% by weight, manganese oxide (MnO) is 5 to 15% by weight, and barium oxide (BaO) is 5 to 20% by weight. Examples of the alkali metal include Li (lithium), Na (sodium), K (potassium), Rb (rubidium), and Cs (cesium), R<sb>2</sb>It is preferable to contain 0 to 8% by weight in terms of O (R is an alkali metal element). Also, Sb<sb>2</sb>O<sb>3</sb>, TeO<sb>2</sb>, ZnO, SiO<sb>2</sb>, A1<sb>2</sb>O<sb>3</sb>, Nb<sb>2</sb>O<sb>5</sb>, La<sb>2</sb>O<sb>3</sb>(La is a rare earth element), Fe<sb>2</sb>O<sb>3</sb>, WO<sb>3</sb>, MoO<sb>3</sb>It is preferable to contain silver in a total of 0 to 25 weight%.</p><p>When the above glass composition is used as a sealing material, filler powder or the like may be mixed in order to obtain desired properties. It is preferable that the mixing amount of the filler powder is 0 to 40% by volume of the total sealing material, and the proportion of the glass composition is 60 to 100% by volume. The filler powder preferably has an average particle diameter of 12 to 40 µm. In particular, it is preferable that the filler is 10 to 30% by volume and the glass composition is 70 to 90% by volume. When used as a sealing material for an image display device, the specific resistance at 25°C after firing the sealing material is 10<sp>10</sp>Ωcm or more is good, and it is preferable that a softening point is 500 degrees C or less. Therefore, the specific resistance of the glass composition is 10<sp>10</sp>Ωcm or more is good, and it is preferable that a softening point is 500 degrees C or less. The image display device of the present invention using the above glass composition for sealing is an image display device having a front plate and a back plate on which electrode wiring is formed, and the front plate and the back plate are hermetically sealed at the periphery. It is characterized in that the above glass composition is used. In particular, for hermetic sealing, it is preferable to use a sealing material composed of 60 to 85% by volume of the glass composition and 15 to 40% by volume of the filler powder. Further, when a wiring material containing silver is used as the electrode wiring, a portion for directly contacting the wiring material with the sealing material of the present invention can be provided. When the glass composition of the present invention is used for a display device, it can be used for electrode wiring, a partition wall, a black layer on the partition wall, and a black band formed on a front plate, in addition to airtight sealing of the display device.</p><p>In addition to the display device, the glass composition can be used for applications requiring adhesion by glass. For example, the glass composition described above can be used as a sealing material for a sheath heater that hermetically seals a terminal and a pipe. It is also possible to mix filler powder with the sealing material of the sheath heater, and it is preferable that the glass composition be 75 to 100% by volume and 0 to 25% by volume of the filler powder. More preferably, the glass composition is 80 to 95% by volume and the filler is 5 to 20% by volume.</p><p>When a metal powder is mixed with the glass composition and used as a wiring material, silver or copper can be used as the metal powder. Moreover, aluminum can also be used. In addition, filler powder may be mixed with the wiring material, and it is preferable to mix the glass composition powder in a ratio of 10 to 40% by volume, the metal powder in a ratio of 60 to 90% by volume, and the filler powder in a ratio of 0 to 20% by volume. By using the above wiring material, electrode wiring of an image display device such as a plasma display panel can be formed. In addition to the display device, it is also applicable to an electrode containing glass such as a solar cell device.</p><p>It is also possible to mix filler powder with the glass composition of the present invention and use it as a structural material such as various glass members. The structural material is preferably mixed in a proportion of 30 to 60% by volume of the glass composition powder and 40 to 70% by volume of the filler powder. By using the above structural material, the partition wall of the image display device can be formed.</p><p>It is possible to use the glass composition of the present invention as a black optical material for controlling the transmittance and reflectance of visible light. Moreover, when using as a black optical material, a filler powder and black pigment powder can be mixed. In that case, it is preferable that the powder of a glass composition sets the component ratio into 60 to 99 volume%, 0 to 40 volume% of a filler powder, and 1 to 30 volume% of black pigment powder. When this black material is used to form the black band of the image display device, a black layer made of the black material is provided on the front plate of the image display device or on the upper part of the partition wall.</p><p>For sealing materials, wiring materials, structural materials, and black materials, if a powder containing a glass composition or the like is used as a paste material mixed with a resin binder and solvent, handling is easy.</p></meansproblemsolution><effectiveness><p>According to the glass composition of the present invention, it is possible to provide a glass composition that can be softened at a low temperature with high practicality without using lead and bismuth. Moreover, it can be applied to various products, and it is possible to provide a product suitable for environmental and safety regulations.</p></effectiveness>

<p>The present invention will be described in more detail. Conventionally, in an image display device, a sealing material in which a filler is mixed with glass that is softened at a low temperature containing lead oxide as a main component has been applied. In recent years, it has become impossible to use lead-containing materials due to environmental and safety regulations.</p><p>In addition, lead-containing glass (low-temperature softened glass) that is softened at a low temperature has been widely applied and developed for sealing electronic devices in addition to hermetic sealing. A glass composition that does not contain lead and softens at a low temperature is required in a wide field of products.</p><p>Lead-free low-temperature softened glass which does not contain lead has a practical problem in the present state. A lead-free low-temperature softened glass containing bismuth as a main component has a higher sealing temperature than a glass containing lead as a main component. Therefore, it is difficult to use it for a product having a member having low heat resistance, such as an electronic device. Also, bismuth is mined in trace amounts as a by-product of lead. Therefore, bismuth is expensive because of its small reserves compared to lead. In addition, since a large amount of lead is released into the world in order to extract the bismuth raw material, there is an indirect influence on the environment and safety. In addition, low-temperature softened glass containing bismuth as a main component is easily reduced, and is difficult to use when heated in an atmosphere with a small amount of oxygen because there is a fear that the electrical resistance may change.</p><p>Glass containing no lead or bismuth and containing tin as a main component has insufficient moisture resistance and the like. In sealing an electronic device such as an image display device, it may be simultaneously fired with a portion (such as a phosphor) containing moisture. At that time, moisture contained in the phosphor material evaporates and the low-temperature softened glass containing tin oxide as a main component is corroded, so that a highly reliable sealing portion cannot be obtained. The cause is that when low-temperature softened glass containing tin as a main component is heat-treated in an oxidizing atmosphere such as in the air, SnO forming the glass skeleton is oxidized and SnO<sb>2</sb>is said to be due to the creation of</p><p>Glass containing no lead or bismuth and containing vanadium as a main component has a problem in that silver wiring and copper wiring are corroded due to the reaction between metal and glass during heat treatment such as sealing. Sufficient consideration has not been given to the interaction with such silver wiring and copper wiring. When the wiring is corroded, problems such as high resistance and generation of bubbles occur. Moreover, the thick film wiring of silver or copper used in electronic devices, such as a plasma display panel, uses glass as a sintering auxiliary agent. The glass containing vanadium could not be used as a sintering aid for wiring since the same problem arises.</p><p>In an image display apparatus for hermetically sealing a front panel and a rear panel such as a plasma display panel (PDP), a glass composition softened at a low temperature is used for hermetic sealing. In an image display apparatus, in addition to hermetic sealing, a glass composition is used as sealing of a member, an electrode material, and a barrier rib material.</p><p>Then, while using lead and bismuth, the present inventors investigated the glass composition which has high practicality and can soften at low temperature. As a result, it was possible to obtain a glass composition substantially free of lead and bismuth, capable of improving environmental and safety considerations, moisture resistance, and mass productivity. Such a glass composition is effective as a sealing material, a structural material, and an optical material. Sealing by the glass composition softened at low temperature is not limited to the image display device as described above, but is also required in various electronic parts such as sheath heaters. Moreover, since this glass has an effect of not corroding wirings of silver, copper, aluminum, etc., it can be used as a sintering auxiliary agent of thick-film wiring, and it can be set as a wiring material.</p><p>An image display device requires a glass composition that is softened at a low temperature in various areas such as sealing, electrodes, and barrier ribs. BACKGROUND ART An image display device such as a plasma display panel has a display panel formed by arranging a front plate and a rear plate to face each other, sealing the periphery to make a vacuum inside, or enclosing a discharge gas. For hermetic sealing, a sealing material made of glass that can be softened at a low temperature of 500° C. or less is used. In the sealing step, the glass paste is applied to the sealing portion of the front plate or the back plate, dried, and then plastically fired in the air, the front plate and the back plate are aligned with a predetermined position and fixed with a chip or the like; heat up Application of the glass paste is performed by a printing method or a dispenser method. In the plasma display panel, after sealing or simultaneously with sealing, the inside of the display panel is exhausted, and the discharge gas is introduced into the inside of the panel. In addition, in a field emission type image display apparatus or an electron emission type image display apparatus, the inside of a panel is made into a high vacuum state during or after hermetic sealing.</p><p>Glass that contains vanadium, phosphorus, manganese, and barium and does not contain lead and bismuth has high moisture resistance and good compatibility with metal materials. Therefore, when an image display device is created using such a glass composition, it has excellent durability and does not corrode wirings such as silver or copper used in mounted electronic devices, so that reliability can be secured for a long period of time. In addition, since lead and expensive bismuth are not used, it is possible to obtain an inexpensive display device while having environmental and safety performance.</p><p>Such a glass composition can be used not only as a sealing part, but also as a wiring material for an image display device such as a plasma display panel, a structural material, and a black material. When using, it is convenient to use it as a paste form. The electrode, barrier rib, and black strip made of the glass composition of the present invention are preferable because they are excellent in durability, have environmental and safety performance, and are inexpensive as in the case of the sealing material. The filler to be mixed with the glass composition is mixed for the purpose of adjusting the coefficient of thermal expansion, adjusting the fluidity at the time of heating, etc. according to the use.</p><p>The glass composition of the present invention can be widely applied and developed to various electronic devices other than display devices. For example, it can be applied to sealing of a sheath heater.</p><p>Hereinafter, the present invention will be described in detail in Examples.</p><p>(Example 1)</p><p>First, various glass compositions capable of being softened at a low temperature of the present invention were prepared. Tables 1 and 2 show the composition and properties of the prepared glass compositions. Both components were expressed by weight ratio in terms of oxides. These glass compositions do not contain lead and bismuth and have a composition containing vanadium and phosphorus as main components. As other components, various components were mixed. Alkali metal and alkaline earth metal (barium, lithium, sodium, cesium) were mixed. Vanadium oxide and phosphorus oxide were used as raw materials, and carbonate was used as raw materials of barium, lithium, sodium, and cesium. BaO is BaPO as raw material<sb>3</sb>may be used. At that time, P<sb>2</sb>O<sb>5</sb> It is necessary to convert by reducing the amount of raw material. Manganese, even if MnO is used as a raw material, MnO<sb>2</sb>may be used. Except for the above components, the oxides shown in Tables 1 and 2 were used as raw materials and blended.</p><p><tables id="1"><img file="KR20090086355A_D0001.tif" /></tables></p><p><tables id="2"><img file="KR20090086355A_D0002.tif" /></tables></p><p>The glass composition was prepared by the following method. 300 g of raw materials obtained by blending and mixing each compound used as raw materials were placed in a crucible, heated in an electric furnace to 1100° C. at a temperature increase rate of 5 to 10° C./min, and maintained for 2 hours. It stirred in order to set it as uniform glass during the holding|maintenance. The crucible was taken out of the electric furnace and poured onto a stainless plate heated in advance to 200 to 300°C. After that, it was pulverized. Differential thermal analysis (DTA) of the glass composition was performed to measure the softening point. The softening point was taken as the second endothermic peak of the DTA curve.</p><p>The pulverized pleated glass composition was made into a glass paste by adding a resin binder and a solvent. Ethyl cellulose was used for the resin binder, and diethylene glycol monobutyl ether acetate was used for the solvent.</p><p>Next, a thick-film glass composition was prepared using the paste. As shown in FIG. 1 , thick-film silver wirings 2 , 3 , and 4 were formed by firing on the upper surface of the glass substrate 1 . The size of the thick silver wiring was 5 μm in thickness, 100 μm in width, and 50 mm in length, and was fired and formed to have an interval of 5 mm. The specific resistance of the thick-film silver wiring at that time was about 10 at a voltage of 100 V at 25°C.<sp>-5</sp>Ωcm. On the thick film silver wiring (2, 3, 4), the thick film silver wiring and glass paste were applied and dried at about 150°C for 2 hours. Thereafter, it was heated to a temperature 30 to 50° C. higher than the softening point at a temperature increase rate of 5° C./min in an electric furnace, maintained for 30 minutes, and then furnace cooled. Thereby, the applied glass paste was fired to form the glass thick films 5, 6, 7, and 8. The glass thick films 5, 6, and 7 had a thickness of 10 µm, a width of 100 µm, and a length of 50 mm, and were spaced at 5 mm intervals. The glass thick film 8 had a thickness of 30 µm, and both width and length were 25 mm, and the thick film silver wirings 2, 3, and 4 were covered.</p><p>The electrical resistance of the thick-film silver wiring (2, 3, 4) and the glass thick-film (5, 6, 7) was respectively measured at 25° C. with a voltage of 100 V to obtain an average resistivity. The specific resistance value was measured using a simple resistance measuring instrument, LotestaAP (manufactured by Vitsubishi Chemical). The average resistivity of the thick film silver wires 2, 3, 4 covering the glass thick film 8 is 10<sp>-5</sp>Ωcm order (1 to 9.9 ×10<sp>-5</sp>Ωcm), , 10<sp>-4</sp>Ωcm order (1 to 9.9×10<sp>-4</sp>Ωcm), , 10<sp>-3</sp>Ωcm order (1 to 9.9×10<sp>-3</sp>Ωcm), , 10<sp>-2</sp>In the case of Ωcm or more, it was evaluated as x because it was difficult to use as wiring. </p><p>Fig. 2 shows the correlation between the resistivity at 25 DEG C of the thick-film glass compositions prepared in Tables 1 and 2 and the resistivity of the thick-film silver wiring covered thereon. The resistivity of a glass composition containing vanadium and phosphorus as main components is 10<sp>9</sp>When it was Ωcm or more, the specific resistance of the thick-film silver wiring was good. In particular, the resistivity of the glass composition is 10<sp>10</sp>When it was more than Ωcm, the resistivity of thick-film silver wiring hardly increased. On the other hand, the resistivity of glass is 10<sp>8</sp>When it is less than Ωcm, the resistivity of the thick-film silver wiring is significantly increased. As a result of finding out this cause, silver and glass reacted, and silver vanadate was produced|generated. When glass with high specific resistance was used, the production|generation of silver vanadate was not confirmed so much. The increase in silver vanadate is thought to be the reason for the change in the resistivity of the thick-film silver wiring. In order to increase the resistivity of the glass composition, it is preferable to contain manganese and barium in addition to the main components vanadium and phosphorus. Furthermore, high resistance can be achieved by containing an alkali metal oxide.</p><p>In addition, when antimony, tellurium, zinc, silicon, aluminum, niobium, and a rare earth element were contained, vitrification stability and chemical stability were improved.</p><p>As a result of comparing various glass compositions, V<sb>2</sb>O<sb>5</sb>is less than 33% by weight, the softening point becomes high, and it becomes unsuitable for sealing at low temperature. On the other hand, V<sb>2</sb>O<sb>5</sb>When is more than 45% by weight, the specific resistance is lowered, and the specific resistance of the wiring is increased by reacting with the silver wiring. P<sb>2</sb>O<sb>5</sb>If it is less than 22 wt%, crystallization is easy, and when it exceeds 30 wt%, the softening point becomes high. When MnO is 5 weight% or less, it is easy to react with silver wiring, and when it exceeds 15 weight%, it becomes easy to crystallize. When BaO was less than 10 wt%, it was easy to crystallize, and when BaO exceeded 20 wt%, the softening point became high. R<sb>2</sb>When O exceeds 8 wt%, the chemical stability deteriorates, and the thermal expansion coefficient becomes too large, resulting in a problem that the glass is peeled off. Sb<sb>2</sb>O<sb>3</sb>, TeO<sb>2</sb>, ZnO, SiO<sb>2</sb>, Al<sb>2</sb>O<sb>3</sb>, Nb<sb>2</sb>O<sb>5</sb>, La<sb>2</sb>O<sb>3</sb>When the total of , crystallization became easy, or the softening point increased at a high temperature.</p><p>Therefore, the preferred composition range of the glass composition is 10<sp>10</sp>Ωcm or more, a softening point of 500° C. or less, a thing which is difficult to crystallize, and a thing with good chemical stability, so that, in terms of oxide, V<sb>2</sb>O<sb>5</sb>33 to 45 wt%, P<sb>2</sb>O<sb>5</sb>22 to 30% by weight of MnO, 5 to 15% by weight of MnO, and 10 to 20% by weight of BaO. Also, R<sb>2</sb>0 to 8% by weight of O (R is an alkali metal element), Sb<sb>2</sb>O<sb>3</sb>, TeO<sb>2</sb>, ZnO, SiO<sb>2</sb>, Al<sb>2</sb>O<sb>3</sb>, Nb<sb>2</sb>O<sb>5</sb>, La<sb>2</sb>O<sb>3 </sb>It is preferable that the sum of at least one of them is 0 to 10% by weight.</p><p>(Example 2)</p><p>In the same manner as in Example 1, further utilizing the insight of Example 1, glass compositions of Table 3 were produced and evaluated. In addition to the glass composition produced in Table 3, the evaluated characteristics are also shown. Neither glass composition contains lead or bismuth and has a composition mainly containing vanadium and phosphorus. As other components, manganese, barium, and alkali metals were contained. In addition, 2 to 4 components of tellurium, zinc, niobium, iron, tungsten, and molybdenum were selected.</p><p><tables id="3"><img file="KR20090086355A_D0003.tif" /></tables></p><p>Using the insights of Example 1, none of the glasses in Table 3 had a resistivity of 10.<sp>9</sp>Ωcm or more, there is little reaction with the silver wiring, and there is little to increase the specific resistance of the silver wiring. However, the glass of No. 76 is V<sb>2</sb>O<sb>5</sb>is less than 30% by weight, and ZnO, Fe<sb>2</sb>O<sb>3</sb>, WO<sb>3</sb>Since the sum of the above was more than 25% by weight, the softening point was high. Glass other than that was as low as 500°C or less.</p><p>As a result of comparing various glass compositions, including the results of Example 1, V<sb>2</sb>O<sb>5</sb>When is less than 30% by weight, it was found that the softening point increased to a high temperature, making it unsuitable for sealing at a low temperature. On the other hand, V<sb>2</sb>O<sb>5</sb>When is more than 45% by weight, the specific resistance was lowered, reacted with the silver wiring, and the specific resistance of the wiring was increased. P<sb>2</sb>O<sb>5</sb>If it is less than 22 wt%, crystallization is easy, and when it exceeds 30 wt%, the softening point becomes high. When MnO is 5 weight% or less, it is easy to react with silver wiring, and when it exceeds 15 weight%, it becomes easy to crystallize. When BaO was less than 5 wt%, crystallization was easy, and when BaO exceeded 20 wt%, the softening point increased. R<sb>2</sb>When O exceeds 8 wt%, the chemical stability deteriorates, and the thermal expansion coefficient becomes too large, resulting in a problem that the glass is peeled off. Sb<sb>2</sb>O<sb>3</sb>, TeO<sb>2</sb>, ZnO, SiO<sb>2</sb>, Al<sb>2</sb>O<sb>3</sb>, Nb<sb>2</sb>O<sb>5</sb>, La<sb>2</sb>O<sb>3</sb>, Fe<sb>2</sb>O<sb>3</sb>, WO<sb>3</sb>, MoO<sb>3</sb>When the total amount of , crystallization became easy, or the softening point increased at a high temperature.</p><p>Therefore, the preferred composition range of the glass composition is 10<sp>9</sp>Ωcm or more, a softening point of 500°C or less, a thing that is difficult to crystallize, and a thing with good chemical stability, so that, in terms of oxide, V<sb>2</sb>O<sb>5</sb>30 to 45 wt%, P<sb>2</sb>O<sb>5</sb>is 22 to 30% by weight, MnO is 5 to 15% by weight, and BaO is 5 to 20% by weight. Also, R<sb>2</sb>0 to 8% by weight of O (R is an alkali metal element), Sb<sb>2</sb>O<sb>3</sb>, TeO<sb>2</sb>, ZnO, SiO<sb>2</sb>, Al<sb>2</sb>O<sb>3</sb>, Nb<sb>2</sb>O<sb>5</sb>, La<sb>2</sb>O<sb>3</sb>, Fe<sb>2</sb>O<sb>3</sb>, WO<sb>3</sb>, MoO<sb>3 </sb>It is preferable that the sum of at least one of them is 0 to 25% by weight. </p><p>(Example 3)</p><p>It carried out similarly to Example 1, and the compatibility of a copper wiring, an aluminum wiring, and the glass composition of Example 1 was examined. The glass used is No. 16, 20, 21, 30 of Table 1, and 42 and 50 of Table 2. Thick copper wiring and aluminum sputter wiring were formed on the substrate in the same manner as in Example 1, and a thick film of the glass composition was formed thereon. In this embodiment, in order to prevent oxidation of the wiring, the glass was fired in a nitrogen atmosphere. As the resin binder of the glass paste, nitrocellulose was used so as to volatilize even in a nitrogen atmosphere.</p><p>In the case of the thick-film copper wiring, the same result as that of the thick-film silver wiring of Example 1 was obtained. The resistivity of glass is 10<sp>8</sp>When it was Ωcm or less, the resistivity of the thick-film copper wiring increased remarkably. As a result of investigating this cause, copper and glass reacted, and copper vanadate was produced|generated. On the other hand, the resistivity of glass is 10<sp>9</sp>If it is more than Ωcm, the resistivity of thick-film copper wiring is good, and in particular, the resistivity of glass is 10.<sp>10</sp>When it was more than Ωcm, the resistivity of thick-film silver wiring hardly increased. Moreover, the production|generation of copper vanadate was not confirmed so much.</p><p>In the case of aluminum sputtered wiring, regardless of the specific resistance of glass containing vanadium oxide and phosphorus oxide as main components, aluminum and glass did not react, and good wiring resistance was obtained.</p><p>(Example 4)</p><p>As Example 4, the type and content of the filler to be mixed into the glass composition were studied. As a filler, powders of β-eucliptite, mullite, amorphous silica, alumina, zirconium silicate, and zirconium phosphate were used. The average particle diameter of the filler was set to 20 to 30 µm. As the glass composition, powders of the glass compositions No. 21 in Table 1 and 42 and 50 in Table 2 were used. The average particle diameter of the glass powder was 5 to 10 µm.</p><p>A glass composition and a filler were mixed to form a paste in the same manner as in Example 1, applied on a glass substrate, dried, and heated at 480° C. in the air for 30 minutes to form a thick film of the glass composition. And fluidity|liquidity and devitrification property during that time were evaluated. When the content of various fillers was 10, 20, 30, 40, or 50 vol%, it was examined. In any of the fillers, the devitrification did not pass up to 40 vol% of the filler content, and appropriate fluidity was exhibited. When the filler content was set to 50% by volume, devitrification occurred and it could not be said that hermetic sealing was possible. Therefore, in the glass composition of the present invention, up to 40% by volume of filler can be mixed and applied as a sealing material.</p><p>When the resistivity of each thick film was confirmed, since all of the fillers used in this example were insulators, the resistivity of the sealing material did not decrease even when mixed with the glass composition.</p><p>In observation at the time of production of the thick film for each example, the difference due to the difference in the glass composition was not largely confirmed. From the difference in fillers, it turned out that especially favorable fluidity|liquidity was shown when mullite, alumina, and zirconium phosphate with a large specific gravity were used. Among them, zirconium phosphate had the best fluidity. Since the glass composition of this invention has vanadium and phosphorus as main components, it is estimated that wettability with a phosphoric acid type filler is favorable.</p><p>Next, compatibility with silver wiring in the case of mixing a filler was examined. Glass compositions No. 21 in Table 1, 42 and 50 in Table 2, and a glass paste containing 30% by volume of filler were prepared, coated on the thick film silver wiring shown in FIG. 1, dried, and heated at 480°C in the air. Heated for 30 minutes. As the filler, mullite, alumina, and zirconium phosphate were used.</p><p>In the same manner as in Example 1, the electrical resistance of the thick-film silver wiring was measured to determine the specific resistance. As a result, almost none of the pastes increased the resistivity of the thick-film silver wiring as in the case of the simple glass of Example 1. That is, it has been confirmed that even a sealing material in which a filler is mixed with a glass composition can be applied to sealing over wiring.</p><p>Moreover, the glass composition which mixed many filler powders was examined. As above-mentioned, in processes, such as baking, it is easy to lose a part of permeation. When the filler powder was 40 to 70% by volume (30 to 60% by volume of the powder of the glass composition), airtight sealing was difficult, but reliable sintering was possible. Therefore, it can be used as a structural material such as a barrier rib of a plasma display panel, not for sealing purposes.</p><p>The glass compositions of Tables 1 and 2 are black. Therefore, it can be used for an optical black member as a black material. Moreover, in order to blacken, you may mix a black pigment with a glass composition. As for content of a black pigment, in order to have high fluidity|liquidity and to prevent devitrification, 30 volume% or less is preferable. Examples of the black member include a black matrix black strip of a plasma display panel.</p><p>(Example 5)</p><p>As Example 5, the particle diameter of the filler mixed with a glass composition was examined. As the glass composition, glass powder No. 42 in Table 2 was used. The coefficient of thermal expansion of No.42 glass is 119×10 in the temperature range of 30°C to 250°C.<sp>-7</sp>/°C. The average particle diameter of the No. 42 glass powder was 7 mu m. The filler content was made constant at 30% by volume. As the filler, zirconium phosphate powder having an average particle diameter of 1, 3, 7, 12, 25, 40, or 50 µm was used. The powder of No.42 glass composition and 30 volume% of zirconium phosphate filler powder were mixed, and the press-molded object was produced. The molded body was heated at 460°C in the air for 30 minutes to prepare a fired body.</p><p>The effect of the particle diameter of the filler on the coefficient of thermal expansion was studied. A 4x4x20 mm sample was produced from the sintered body by machining, and it was set as a thermal expansion measurement sample. A thermal expansion curve was measured at a temperature increase rate of 5° C./min using a thermal expansion meter. The coefficient of thermal expansion was obtained in a temperature range of 30 °C to 250 °C. The relationship between the average particle diameter of a filler and the coefficient of thermal expansion after filler inclusion in FIG. 3 is shown. Simultaneously with the increase of the particle diameter, the coefficient of thermal expansion decreased. The method of the reduction decreased sharply to 12 μm, and gradually decreased beyond that. However, cracks occurred in the glass at 50 µm. Therefore, in order to reduce the coefficient of thermal expansion efficiently by mixing a filler, it turned out that a preferable filler average particle diameter is 12-40 micrometers.</p><p>(Example 6)</p><p>In Example 6, an example in which the glass composition of the present invention was applied to a wiring material for forming a metal thick-film wiring was studied. The wiring is formed by firing a wiring material comprising a glass composition powder, a metal powder for forming the wiring, a resin binder, and a solvent. In this Example, No. 42 glass of Table 2 was used as a glass composition. As is clear from the table, No. 42 glass is difficult to increase the specific resistance of silver. Ethyl cellulose was used as a binder and diethylene glycol monobutyl ether acetate was used as a solvent.</p><p>The glass composition powder was mixed with the silver powder, and the paste for wiring was produced by adding a resin binder and a solvent. </p><p>Similarly, a paste for wiring in which the volume ratio of the glass composition powder and the silver powder was appropriately changed was produced. Using the prepared paste for wiring, the paste was applied on a glass substrate by a printing method, and heated at 480° C. in the air for 30 minutes to form wiring.</p><p>The resistance value of the produced wiring was measured, and the specific resistance was calculated|required. Fig. 4 shows the relationship between the silver content and the specific resistance of the wiring. In a wiring having a silver content of 60 vol% or more (a glass composition content of 40 vol% or less), the specific resistance of the wiring is sufficiently low. Therefore, by setting the content of the glass composition to 40% by volume or less, the glass composition of the present invention can be used as a wiring material.</p><p>When content of the glass in wiring is reduced, silver wiring will become easy to peel from a board|substrate. When the content of the glass composition was 10% by volume or more, the silver wiring could be firmly formed on the glass substrate. Moreover, when the various fillers examined in Example 3 were mixed with a wiring material, it became difficult to peel a silver wiring. Since the specific resistance increases when the filler is mixed, an appropriate mixing amount is 20% by volume or less. That is, it can be effectively used as a wiring material by setting the content of the glass composition to be 10 to 40% by volume, the content of the silver powder to be 60 to 90% by volume, and the content of the filler to be 0 to 20% by volume.</p><p>Similarly, copper thick-film wiring was studied. As a glass composition, glass of No. 55 of Table 2 was used, glass powder and copper powder were mixed, and the paste for wiring was produced by adding a binder and a solvent. Nitrocellulose was used for the resin binder, and diethylene glycol monobutyl ether acetate was used for the solvent. The produced wiring paste was applied to a glass substrate by a printing method, and heated at 600° C. in nitrogen for 30 minutes to form wiring. As a result of measuring the resistance value of the formed wiring, the same result as the above-mentioned silver wiring material was obtained. Therefore, the glass composition of the present invention can be applied in addition to the silver wiring material.</p><p>However, the resistivity is 10<sp>9</sp>In the case of the glass of less than Ωcm, the specific resistance of the wiring is remarkably increased as in Example 1 due to the reaction with the wiring.</p><p>(Example 7)</p><p>Using the glass Nos. 68, 71 and 73 of Table 3, in the same manner as in Example 6, silver, copper, and aluminum thick-film electrode wirings were studied. A paste for electrode wiring was prepared by mixing 10% by volume of each glass powder and 90% by volume of powder of silver, copper, and aluminum, respectively, and adding a binder and a solvent. As the powder of silver, copper and aluminum, a mixture of a spherical powder having a diameter of about 1 μm and a plate-like powder crushed thereto was used in a 1:1 ratio. As the resin binder, ethyl cellulose was used for silver and aluminum, and nitrocellulose was used for copper. Diethylene glycol monobutyl ether acetate was used as the solvent. The produced paste for electrode wiring was applied to a glass substrate by a printing method, and was heated at 500° C. for 30 minutes for silver and aluminum in the air and for copper in nitrogen in nitrogen to form wiring. As a result of measuring the resistance value of the formed wiring, the same result as Example 6 was obtained. Therefore, the glass composition of the present invention can be effectively applied to thick film electrode wiring of silver, copper, and aluminum.</p><p>(Example 8)</p><p>As Example 8, an example in which the glass composition of the present invention is applied to a plasma display panel will be described. The outline of the cross-sectional view of a plasma display panel is shown in FIG.</p><p>In the plasma display panel, the front plate 10 and the rear plate 11 are disposed to face each other with a gap of 100 to 150 mu m, and the gap between the respective substrates is held by a partition wall 12 . The peripheral edges of the front plate 10 and the rear plate 11 are hermetically sealed with a sealing material 13, and the inside of the panel is filled with a rare gas. Red, green, and blue phosphors 15, 16, and 17 are respectively filled in the microcavity (cell 14) separated by the partition wall 12, and one pixel is composed of cells of three colors. Each color of light is emitted accordingly.</p><p>On the front plate 10 and the rear plate 11, electrodes arranged regularly on a glass substrate are provided. The display electrode 18 of the front panel 10 and the address electrode 19 of the rear panel 11 are paired, and a voltage of 100 to 200 V is selectively applied according to a display signal therebetween, and a discharge between the electrodes is applied. UV light 20 is generated, the phosphors 15, 16, and 17 are emitted, and image information is displayed. The display electrode 18 and the address electrode 19 are covered with dielectric layers 22 and 23 for protection of these electrodes and control of wall charges during discharge.</p><p>In the rear plate 11 , barrier ribs 12 are provided on the dielectric layers 23 of the address electrodes 19 to form the cells 14 . This partition 12 is a stripe-shaped or box-shaped structure. Also, in order to improve contrast, a black matrix (black band) 21 may be formed between the display electrodes of adjacent cells.</p><p>As the display electrode 18 and the address electrode 19, a silver thick film wiring is generally used now. In addition, for a countermeasure against silver migration, a change from a silver thick film wiring to a copper thick film wiring is being considered. For that purpose, countermeasures against oxidation of copper are required. The display electrode 18 , the address electrode 19 , and the black matrix 21 may be formed by sputtering, but the printing method is advantageous for cost reduction. The dielectric layers 22 and 23 are generally formed by a printing method.</p><p>In the front panel 10, after the display electrodes 18 and the black matrix 21 are formed so as to be orthogonal to the address electrodes 19 of the rear panel 11, the dielectric layer 22 is formed over the entire surface. A protective layer 24 is formed on the dielectric layer 22 to protect the display electrode 18 and the like from electric discharge. In general, for the protective layer 24, a vapor deposition film of MgO is used. In the rear plate 11 , a partition 12 is provided on the address electrode 19 and the dielectric layer 23 . The partition wall made of a glass structure is made of a structural material containing at least a glass composition and a filler, and is constituted of a fired body obtained by sintering the structural material. The partition wall 12 is formed by attaching a volatile sheet with a cut groove to the partition wall portion, pouring the partition wall paste into the groove, and firing at 500 to 600° C. to volatilize the sheet and form the partition wall 12 at the same time. have. In addition, the barrier rib 12 may be formed by applying the barrier rib paste to the entire surface by a printing method, masking after drying, removing unnecessary portions by sand blasting or chemical etching, and firing at 500 to 600°C. In the cells 14 separated by the partition wall 12, pastes of the phosphors 15, 16, and 17 of each color are respectively filled, and the phosphors 15, 16, and 17 are respectively filled by firing at 450 to 500°C. to form</p><p>Usually, the front plate 10 and the back plate 11 which were respectively produced are made to oppose, and they are precisely aligned, and the peripheral part is glass-sealed at 420-500 degreeC. The sealing material 13 is previously formed on the peripheral edge of either the front plate 10 or the rear plate 11 by a dispenser method or a printing method. In general, the sealing material 13 is formed on the back plate 11 side. In addition, the sealing material 13 may be pre-fired simultaneously with the firing of the phosphors 15, 16, and 17. By taking this method, bubbles in the glass sealing portion can be remarkably reduced, and a high airtightness, that is, a highly reliable glass sealing portion is obtained. In the glass sealing, the gas inside the cell 14 is exhausted while heating, and the rare gas is sealed, and the panel is completed. When the sealing material 13 is plastically fired or glass is sealed, the sealing material 13 may come in direct contact with the display electrode 18 or the address electrode 19, and may be sealed with a wiring material such as silver forming the electrode. It is undesirable for the material 13 to react to increase the electrical resistance of the wiring material, and it is necessary to prevent this reaction. For that purpose, it is necessary to prevent the glass composition contained in the sealing material 13 from reacting with the wiring material.</p><p>In order to light up the completed panel, a voltage is applied at the intersection of the display electrode 18 and the address electrode 19 to discharge the rare gas in the cell 14 to put it into a plasma state. Then, the phosphors 15, 16, and 17 are made to emit light by using the ultraviolet rays 20 generated when the rare gas in the cell 14 returns from the plasma state to the original state to light the panel and display image information. do. When each color is lit, an address discharge is performed between the display electrode 18 and the address electrode 19 of the cell 14 to be lit, and wall charges are accumulated in the cell. Next, by applying a constant voltage to the display electrode pair, the display discharge occurs only in the cells in which the wall charges are accumulated by the address discharge, and the ultraviolet light 20 is generated to display the image information in a structure in which the phosphor emits light.</p><p>The mixture of filler and glass composition studied in Example 4 was used as a sealing material and applied to the plasma display panel shown in FIG. The thermal expansion coefficient of the sealing material is 70 to 75 × 10 by adjusting the mixing ratio of the filler.<sp>-7</sp>/°C. In addition, the coefficient of thermal expansion of the glass substrate used for the front plate 10 and the rear plate 11 is 80 to 85 × 10<sp>-7</sp>Since glass of /°C is used, the thermal expansion coefficient of the sealing material is 10 to 15% smaller than that of the glass substrate, and compressive stress is applied to the sealing material 13 . </p><p>First, the glass powder of No. 42 in Table 2 and the filler powder of zirconium phosphate were mixed. The mixing ratio was 70 vol% of No. 42 glass powder and 30 vol% of filler powder. The particle diameter was made into 7 micrometers in the average particle diameter of the glass powder of No. 42, and 30 micrometers in the average particle diameter of the zirconium phosphate filler powder. To these powders, a resin binder (ethyl cellulose) and a solvent (diethylene glycol monobutyl ether acetate) were mixed to prepare a sealing paste. The thermal expansion coefficient of this paste after firing is 72 × 10<sp>-7</sp>/°C. </p><p>This paste was applied to the peripheral edge of the back plate 11 by a dispenser method. After drying at 200°C, it was calcined at 480°C in the air for 30 minutes. The rear plate 11 and the front plate 10 were precisely opposed to each other, fixed with a clip, heated to 450° C. while exhausted, and maintained for 3 hours, then filled with a rare gas and cooled. I was able to seal it confidentially without any problems. There was no problem in the panel lighting test.</p><p>Similar to the glass of No. 42, using the glass powder of Nos. 16, 20, 21, 30 of Table 1, and 50 of Table 2, a plasma display panel was tested. As fillers, powders of β-eucliptite, mullite, amorphous silica, alumina, zirconium silicate, and zirconium phosphate were used, and sealing was performed by changing the filler content. The thermal expansion coefficient of either sealing material is 70 to 75 × 10<sp>-7</sp>The filler was adjusted so that it might become /degreeC.</p><p>As a result, regardless of the type of filler, the appropriate content of the filler in the sealing portion was 15 to 40% by volume (the content of the glass composition was 60 to 85% by volume). When the filler content is less than 15% by volume, the sealing material is sucked into the inside of the panel at the time of sealing and exhausting, so that airtightness cannot be maintained or the sealing becomes uneven. In addition, when the filler content exceeds 40% by volume, the sealing material is not properly crushed even under reduced pressure, resulting in a further lack of adhesive force in some cases.</p><p>Next, for the display electrode 18 of the front plate 10 and the address electrode 19 of the rear plate 11, the glass powder No. 42 in Table 2 was used. Using a wiring material consisting of No. 42 glass powder in 15 vol%, zirconium phosphate filler powder in 5 vol%, and silver powder by 80% by volume, paste it to produce wiring, and test the panel in the same manner as above. produced. There was no problem in particular, and it was able to mount on the panel as wiring. Also, there was no problem in the panel lighting test. Therefore, the above-described glass composition can be used for the display electrode 18 or the address electrode of the plasma display panel.</p><p>Next, the glass powder No. 42 in Table 2 was used for the partition wall 12 . No. 42 glass powder was mixed in a ratio of 40% by volume, mullite filler powder at 30% by volume, and alumina filler powder at a ratio of 30% by volume to be a structural material for the partition wall, and a panel was tested in the same manner as above. Even when used for the partition wall, there was no problem in the manufacture of the panel, and there was no problem in the panel lighting test. Therefore, it can also be used for the barrier rib 12 of a plasma display panel.</p><p>Next, the glass powder No. 42 in Table 2 was used for the black matrix 21 . A black material was obtained by mixing 60% by volume of the glass powder of No.42, 30% by volume of amorphous silica filler powder, and 10% by volume of a black pigment powder, and a panel was tested in the same manner as above. Even when used for a black matrix, there was no problem in the production of the panel, and there was no problem in the panel lighting test.</p><p>(Example 9)</p><p>This embodiment describes an example in which the glass composition is applied to the hermetic sealing of the sheath heater. Fig. 6 shows the schematic structure of a typical sheath heater. A sheath heater is generally a stainless steel U-shaped pipe 30, with magnesium oxide powder 31 and a stainless steel terminal 33 connected to the heater 32, and both ends are connected with a sealing material 34. It has a structure in which it is hermetically sealed with pellets made of</p><p>First, the magnesium oxide powder 31 and the stainless steel terminal 33 were put into a stainless steel U-shaped pipe, and the magnesium oxide powder was heated and dehydrated in a reducing atmosphere. Pellets made of a sealing material were placed at both ends and heated to seal both ends hermetically. The thermal expansion coefficient of the sealing material is 110 to 130 × 10 according to the stainless steel.<sp>-7</sp>It is preferable to set it as about / degreeC. Therefore, filler content for adjusting a thermal expansion coefficient was made into 25 volume% or less. When the filler was mixed in more than 25% by volume, the coefficient of thermal expansion became low and it became difficult to seal in an airtight manner.</p><p>A sealing material composed of 80% by volume of the glass powder of No.42 in Table 2 and 20% by volume of alumina filler powder was used as pellets, installed at the tip of a sheath heater, and heated at 480°C for 10 minutes in a nitrogen atmosphere. There was no problem in particular, and airtight sealing was possible. In addition, the continuous heating test (100°C) for 50 days was suitable without electrical short circuiting between the pipe and the terminal or damage to the sealing part.</p><p>(Example 10)</p><p>The plasma display panel of FIG. 5 was produced similarly to Example 8 using the 3 types of silver electrode wiring pastes studied in Example 7. The three silver electrode wiring pastes used contained 90 vol% of spherical and plate-shaped mixed silver powder and 10 vol% of glass powder of Nos. 68, 71 and 73 in Table 3, respectively. In addition, ethyl cellulose is used as a resin binder, and diethylene glycol monobutyl ether acetate is used as a solvent. In addition, in this example, the paste contained a photosensitizer.</p><p>These electrode wiring pastes are used to apply and dry the entire surfaces of the front plate 10 and the rear plate 11, attach a mask and irradiate with ultraviolet rays to remove excess portions, and display electrodes 18 and rear surfaces. A plate 11 was formed. Then, it baked at 500 degreeC for 30 minutes. Next, the black matrix 21 and the dielectric layers 22 and 23 were respectively formed at 500 to 600 DEG C, and a plasma display panel was manufactured in the same manner as in the ninth embodiment. Further, for sealing the front plate 10 and the rear plate 11, the sealing material containing 70% by weight of the glass powder No.71 in Table 3, 20% by volume of cordierite as a filler, and 10% by volume of alumina was used, and ethyl cellulose and diethylene glycol monobutyl ether acetate were added thereto to obtain a sealing paste, and sealing was performed in the same manner as in Example 9.</p><p>The three types of plasma display panels produced by using the above three types of silver electrode wiring pastes were able to be produced without any problem in particular in terms of processes in any of the panels. Moreover, generation|occurrence|production of a problem was not confirmed also in the panel lighting test. Therefore, the silver thick-film electrode wiring can be applied to the display electrode 18 and the address electrode 19 of the plasma display panel, and the glass composition of the present invention is also effective for the silver thick-film wiring.</p><p>(Example 11)</p><p>In Example 11, an example in which a wiring material containing the glass composition of the present invention is applied to an electrode of a solar cell element will be described. A cross-sectional view of a typical solar cell element, and an outline of a light-receiving surface and a back surface are shown in FIGS. 7, 8 and 9 . Usually, single crystal or polycrystalline silicon is used for the semiconductor substrate 40 of the solar cell device. This semiconductor substrate 40 contains boron or the like and is made of a p-type semiconductor. On the light-receiving surface side, in order to suppress reflection of sunlight, the unevenness|corrugation is formed by etching. The light-receiving surface is doped with phosphorus or the like to form an n-type semiconductor diffusion layer 41 with a thickness of submicron order, and a pn junction is formed at the boundary with the p-type bulk portion. In addition, an antireflection layer 42 made of silicon nitride or the like is formed on the light receiving surface to have a thickness of about 100 nm by vapor deposition or the like.</p><p>Next, the formation of the light-receiving surface electrode 43 formed on the light-receiving surface, and the current collecting electrode 44 and the output extraction electrode 45 formed on the back surface will be described. Usually, a silver electrode paste containing a powder of a glass composition is used for the light-receiving surface electrode 43 and the output extraction electrode 45, and an aluminum electrode paste containing a powder of a glass composition is used for the current collecting electrode 44, and is applied by screen printing. do. After drying, it is baked at about 500-800 degreeC, and an electrode is formed. At that time, on the light-receiving surface, the glass composition contained in the light-receiving surface electrode 43 and the antireflection layer 42 react, and the light-receiving surface electrode 43 and the diffusion layer 41 are electrically connected. Further, on the back side, aluminum in the current collecting electrode 44 diffuses on the back surface of the semiconductor substrate 40 to form an electrode component diffusion layer 46, thereby forming the semiconductor substrate 40, the current collecting electrode 44, and the power withdrawal electrode ( 45) and ohmic contact can be obtained.</p><p>Using the powder of the glass composition No. 71 in Table 3, silver electrode pastes for the light-receiving surface electrode 43 and the power extraction electrode 45 and the aluminum electrode paste for the current collecting electrode 44 were prepared. The content of the powder of the No. 71 glass composition was 10% by volume, and powders of silver and aluminum were respectively blended and mixed so as to be 90% by volume. The average particle diameter of the powder of the No. 71 glass composition was about 1 µm. As the powder of silver and aluminum, a spherical powder having a diameter of about 1 to 3 µm was mechanically crushed to obtain a plate-like powder. Ethyl cellulose was used for the resin binder and diethylene glycol monobutyl ether acetate was used for the solvent, and a paste having a viscosity suitable for screen printing was obtained.</p><p>First, the aluminum electrode paste for the current collecting electrode 44 was applied to the back surface of the semiconductor substrate 40 by screen printing as shown in FIGS. 7 and 9, dried, and rapidly heated and cooled to 550° C. in an infrared furnace. . The holding time at 550°C was 3 minutes. Accordingly, first, the current collecting electrode 44 was formed on the back surface of the semiconductor substrate 40 .</p><p>Next, the light-receiving surface of the semiconductor substrate 40 on which the diffusion layer 41 and the antireflection layer 42 are formed, and the back surface of the semiconductor substrate 40 on which the current collecting electrode 44 is already formed, by screen printing, 7, 8, and 9, after apply|coating and drying, it rapidly heat-cooled at 700 degreeC in an infrared furnace. The holding time was set to 1 minute.</p><p>In the produced solar cell element, on the light-receiving surface, the light-receiving surface electrode 43 and the semiconductor substrate 40 on which the diffusion layer 41 was formed were electrically connected. In addition, the electrode component diffusion layer 46 was formed on the back surface, and an ohmic contact was obtained between the semiconductor substrate 40 and the current collecting electrode 44 and the power extraction electrode 45 . In addition, the high-temperature, high-humidity test at 85°C and 85% was conducted for 100 hours, and there was hardly any increase in the wiring resistance or contact resistance of the electrode.</p><p>The glass compositions of Nos. 62, 67, 73 and 75 of Table 3 were also assembled into silver thick-film electrodes or aluminum thick-film electrodes of a solar cell element and evaluated in the same manner as above. Those evaluation results were equivalent to the glass composition of No. 71 described above. Therefore, the glass composition of the present invention can be effectively deployed on the electrode of a solar cell element.</p>