Glass composition, sealing material, and sealing material paste

Abstract

Provided are a glass composition, sealing material, and sealing material paste that enable sealing at low temperatures while having good weather resistance.　The glass composition of the present invention is characterized by comprising 15-80 mol% TeO2, 0.1-30 mol% MoO3, 5-40 mol% V2O5, 0.1-10 mol% Nb2O5, and 2.1-10 mol% ZrO2 as the composition of the glass.

Description

Glass composition, sealing material, and sealing material paste

[0001] The present invention relates to a glass composition, a sealing material, and a sealing material paste that are weather-resistant and capable of airtight sealing at low temperatures.

[0002] Sealing materials are used in semiconductor integrated circuits, quartz oscillators, metal components, vacuum insulated glass, flat-panel displays, and LED glass terminals. Because sealing materials require chemical durability and heat resistance, glass-based sealing materials are used rather than resin-based adhesives. Sealing materials also require properties such as mechanical strength, fluidity, and weather resistance. In particular, for sealing electronic components that house heat-sensitive elements, it is necessary to keep the sealing temperature as low as possible. Specifically, it is required that sealing is possible at temperatures of 400°C or below. Lead borate-based glass containing a large amount of PbO, which has a significant effect in lowering the softening point, has been widely used as a glass that satisfies this property (see, for example, Patent Document 1).

[0003] Japanese Patent Publication No. 63-315536, Japanese Patent Publication No. 2019-202921

[0004] To reduce environmental impact, there is a desire to replace lead-borate glass with lead-free glass that does not contain PbO, and various types of lead-free glass with low softening points have been developed.

[0005] However, generally speaking, glass with a low softening point has poor weather resistance, resulting in problems such as cracking of the glass. Therefore, achieving both a low softening point and high weather resistance is not easy. (CuO-TeO as described in Patent Document 2) ２ -MoO ３ While lead-borate glass is a promising alternative to lead-borate glass and possesses good weather resistance, its softening point is not sufficiently low.

[0006] In view of the above, the present invention aims to provide a glass composition, a sealing material, and a sealing material paste that have good weather resistance and can be sealed at low temperatures.

[0007] As a result of diligent research, the inventors have determined a predetermined TeO ２ - MoO ３ -V ２ O ５It has been found that the above problems can be solved by using a certain glass, and it is proposed as the present invention. Hereinafter, each aspect of the glass composition and the sealing material will be described.

[0008] The glass composition of Aspect 1 has, as a glass composition, in mol%, TeO ２ 15 to 80%, MoO ３ 0.1 to 30%, V ２ O ５ 5 to 40%, Nb ２ O ５ 0.1 to 10%, ZrO ２ 2.1 to 10% and is characterized by containing these.

[0009] The glass composition of Aspect 2, in Aspect 1, in mol%, contains CuO 0.1 to 35%, Al ２ O ３ 0.1 to 10%, K ２ O 1 to 30%, PbO 0 to 10%, and preferably does not substantially contain SeO ２ Here, "does not substantially contain SeO ２ " means that the content of SeO ２ is less than 0.1 mol%.

[0010] The glass composition of Aspect 3, in Aspect 1 or 2, has, as a glass composition, in mol%, Li ２ O + Na ２ O 0.1 to 15%, and preferably has a molar ratio of (Li ２ O + Na ２ O) / K ２ O of 0.05 to 1. Here, "Li ２ O + Na ２ O" is the total amount of Li ２ O and Na ２ O. "(Li ２ O + Na ２ O) / K ２ O" is the value obtained by dividing the total amount of Li ２ O and Na ２ O by the content of K ２ O.

[0011] The glass composition of Embodiment 4 preferably contains, in any one embodiment of Embodiments 1 to 3, 0.1 to 20% in mol% of MgO + CaO + SrO + BaO + ZnO as the glass composition. Here, "MgO + CaO + SrO + BaO + ZnO" is the total amount of MgO, CaO, SrO, BaO, and ZnO.

[0012] The glass composition of embodiment 5, in any one embodiment from embodiment 1 to embodiment 4, has a glass composition of La in mol%. ２ O ３ It is preferable that it contains 0 to 10%.

[0013] The sealing material of embodiment 6 preferably contains 40 to 100% by volume of glass powder made from a glass composition of any one embodiment from embodiment 1 to embodiment 5, and 0 to 60% by volume of refractory filler powder.

[0014] In the sealing material of embodiment 7, it is preferable that the refractory filler powder is substantially spherical in shape, as in embodiment 6. Here, "substantially spherical" is not limited to a perfect sphere, but refers to refractory filler powder in which 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.

[0015] The sealing material of embodiment 8 is characterized in that, in embodiment 6 or 7, all or part of the fire-resistant filler powder is Zr ２ WO ４ (PO ４ ) ２ It is preferable that this be the case.

[0016] The sealing material of embodiment 9 is preferably used in a quartz crystal oscillator package in any one of embodiments 6 to 8.

[0017] The sealing material of embodiment 10 is preferably used in vacuum insulated glass in any one of embodiments 6 to 8.

[0018] The sealing material paste of embodiment 11 preferably contains the sealing material and vehicle of any one embodiment of embodiments 6 to 10.

[0019] The present invention can provide a glass composition, a sealing material, and a sealing material paste that have good weather resistance and can be sealed at low temperatures.

[0020] This is a schematic diagram showing the measurement curve obtained by a macro-type differential thermal analyzer.

[0021] The glass composition of the present invention has a glass composition of TeO in mol%. ２ 15-80%, MoO ３ 0.1-30%, V ２ O ５ 5-40%, Nb ２ O ５ 0.1-10%, ZrO ２ It contains 2.1-10%. The reason for limiting the glass composition range as described above is explained below. In the explanation of the content of each component, unless otherwise specified, "%" means "mol%".

[0022] TeO ２ It is a component that forms a glass network and enhances weather resistance. ２ The content is 15-80%, preferably 20-70%, 25-60%, and particularly preferably 30-50%. ２ If the content of TeO is too low, the glass becomes thermally unstable and is prone to devitrification during melting or firing. ２ If the content is too high, the viscosity of the glass (softening point, etc.) increases, making low-temperature sealing difficult, and the coefficient of thermal expansion tends to become too high.

[0023] MoO ３ It is a component that forms a glass network and also reduces the viscosity (softening point, etc.) of the glass. ３ The content is 0.1 to 30%, preferably 0.5 to 20%, 1 to 10%, and particularly preferably 1.5 to 5%. ３ If the content is too low, vitrification becomes difficult, and the viscosity of the glass (softening point, etc.) increases, making low-temperature sealing difficult. On the other hand, MoO ３ If the content of is too high, the glass becomes thermally unstable, making it more prone to devitrification during melting or firing, and the coefficient of thermal expansion tends to become too high.

[0024] V ２ O ５ It is a component that forms a glass network and reduces the viscosity (softening point, etc.) of the glass. It is also a component that reduces the coefficient of thermal expansion. V ２ O ５ The content is 5-40%, preferably 7-35%, 10-30%, 13-29%, and particularly preferably 16-28%. ２ O ５ If the content is too low, vitrification becomes difficult, and the viscosity of the glass (softening point, etc.) increases, making low-temperature sealing difficult. Also, the coefficient of thermal expansion tends to become too high. On the other hand, V ２ O ５ If the content is too high, the glass becomes thermally unstable, and it is more prone to devitrification during melting or firing.

[0025] Nb ２ O ５ Nb is a component that thermally stabilizes glass and enhances its weather resistance. ２ O ５ The content is 0.1 to 10%, preferably 0.3 to 5%, 0.5 to 4%, and particularly preferably 0.7 to 2%. ２ O ５ If the content of is too low, the glass becomes thermally unstable, and it is more prone to devitrification during melting or firing. Furthermore, its weather resistance decreases, resulting in increased cracking of the glass. On the other hand, Nb ２ O ５ If the content is too high, the viscosity (softening point, etc.) of the glass increases, making low-temperature sealing difficult.

[0026] ZrO ２ This component thermally stabilizes the glass and enhances its weather resistance. It also reduces the coefficient of thermal expansion. ZrO ２ The content is preferably 2.1 to 10%, 2.2 to 8%, and particularly preferably 2.3 to 6%. ２ If the content is too low, weather resistance decreases, and as a result, the glass becomes more prone to cracking. Also, the water resistance of the sealing interface tends to decrease. On the other hand, ZrO ２If the content is too high, the viscosity (softening point, etc.) of the glass increases, making low-temperature sealing difficult.

[0027] In addition to the above ingredients, the following ingredients may also be included.

[0028] CuO is a component that reduces the viscosity (softening point, etc.) and thermal expansion coefficient of glass. It also increases the adhesive strength between glass and metal when sealing metals. While the mechanism by which it increases adhesive strength is not yet fully understood, it is thought that because Cu atoms are highly diffusive, they diffuse from the surface to the interior of the metal, making it easier for the glass and metal to integrate. There are no particular restrictions on the type of metal to be sealed, but examples include iron, iron alloys, nickel, nickel alloys, copper, copper alloys, aluminum, and aluminum alloys. The CuO content is preferably 0-35%, 0.1-35%, 5-33%, 7-30%, 10-25%, and particularly preferably 13-20%. If the CuO content is too low, vitrification becomes difficult, the viscosity (softening point, etc.) of the glass increases, and low-temperature sealing becomes difficult. Furthermore, the thermal expansion coefficient tends to become too high. If the CuO content is too high, the glass becomes thermally unstable, and during the sealing process, metallic Cu may precipitate from the glass surface, potentially negatively affecting the sealing strength and electrical properties. Furthermore, the glass becomes more prone to devitrification during melting or firing.

[0029] Al ２ O ３ Al is an ingredient that improves weather resistance. ２ O ３ The content of is preferably 0-10%, 0.1-10%, 0.3-8%, 0.5-6%, and especially preferably 1-4%. ２ O ３ If the content is too low, the weather resistance of the glass will decrease, and as a result, the glass will be more prone to cracking. ２ O ３ If the content is too high, the viscosity (softening point, etc.) of the glass increases, making low-temperature sealing difficult.

[0030] Li ２ O, Na ２ O and K ２O is a component that reduces the viscosity (softening point, etc.) of the glass. Li ２ O + Na ２ O + K ２ The content of O is preferably 0 to 30%, 1 to 30%, 5 to 25%, 7 to 23%, particularly 10 to 20%. Li ２ O + Na ２ O + K ２ If the content of O is too low, the viscosity (softening point, etc.) of the glass may increase, making it difficult to seal at low temperatures. Also, it may be difficult to vitrify. On the other hand, Li ２ O + Na ２ O + K ２ If the content of O is too high, the glass becomes thermally unstable, and the glass is likely to devitrify during melting or firing. Also, the weather resistance and the water resistance of the sealing interface tend to decrease, and the thermal expansion coefficient tends to become too high. Also, Li ２ O + Na ２ The content of O is preferably 0 to 15%, 0.1 to 15%, 1 to 12%, particularly 2 to 10%.

[0031] Li ２ O is a component that reduces the viscosity (softening point, etc.) of the glass. Li ２ The content of O is preferably 0 to 15%, 0.1 to 12%, 1 to 8%, particularly 1.5 to 5%. Li ２ If the content of O is too low, the viscosity (softening point, etc.) of the glass may increase, making it difficult to seal at low temperatures. Also, it may be difficult to vitrify. On the other hand, Li ２ If the content of O is too high, the glass becomes thermally unstable, and the glass is likely to devitrify during melting or firing. Also, the weather resistance tends to decrease, and the thermal expansion coefficient tends to become too high.

[0032] Na ２ O is a component that reduces the viscosity (softening point, etc.) of the glass. Na ２ The content of O is preferably 0 to 15%, particularly 0.1 to 5%. Na ２ If the content of O is too low, the viscosity (softening point, etc.) of the glass may increase, making it difficult to seal at low temperatures. Also, it may be difficult to vitrify. On the other hand, Na ２If the oxygen content is too high, the glass becomes thermally unstable, and devitrification is more likely to occur during melting or firing. Furthermore, weather resistance tends to decrease, and the coefficient of thermal expansion tends to become excessively high.

[0033] K ２ O is Li ２ O and Na ２ Compared to O, this component reduces the viscosity (softening point, etc.) of glass without significantly reducing its weather resistance. ２ The O content is preferably 0-30%, 1-30%, 3-25%, 5-22%, and particularly 10-20%. ２ If the O content is too low, the viscosity (softening point, etc.) of the glass will increase, making sealing at low temperatures difficult. It may also become difficult to vitrify. Furthermore, weather resistance will decrease, resulting in the glass becoming more prone to cracking. On the other hand, K ２ If the oxygen content is too high, the glass becomes thermally unstable, making it prone to devitrification during melting or firing.

[0034] In molar ratio, (Li ２ O + Na ２ O) / K ２ In order to reduce the viscosity (softening point, etc.) of the glass without significantly reducing its weather resistance, O is preferably 0.05 to 1, 0.08 to 0.6, and particularly 0.1 to 0.3.

[0035] PbO is a component that reduces the viscosity (softening point, etc.) of glass. However, considering environmental factors, the PbO content should be 0-10%, preferably 0-5%, 0-3%, 0-1%, or even substantially absent (less than 0.1%).

[0036] SeO ２ It is a component that lowers the viscosity (softening point, etc.) of glass, but considering the environmental aspects, SeO ２ The content of is preferably 0-10%, 0-5%, 0-3%, 0-1%, or even less than 0.1%.

[0037] MgO, CaO, SrO, BaO, and ZnO are components that broaden the vitrification range and improve weather resistance. The preferred concentrations of MgO + CaO + SrO + BaO + ZnO are 0-30%, 0.1-20%, 1.2-15%, 1.5-12%, and particularly 1.5-5%. If the content of MgO + CaO + SrO + BaO + ZnO is too low, the viscosity of the glass (softening point, etc.) will increase, making sealing at low temperatures difficult. It may also become difficult to vitrify. On the other hand, if the content of MgO + CaO + SrO + BaO + ZnO is too high, the glass will become thermally unstable, and it will be more prone to devitrification during melting or firing. It may also be more prone to reduced weather resistance and an excessively high coefficient of thermal expansion.

[0038] MgO is a component that broadens the vitrification range and improves weather resistance. The MgO content is preferably 0-25%, 0-20%, 0-10%, and especially 0.1-3%. If the MgO content is too low, vitrification may become difficult. Also, the viscosity of the glass (softening point, etc.) may increase, making sealing at low temperatures difficult. On the other hand, if the MgO content is too high, the glass becomes thermally unstable, and it is more likely to devitrify during melting or firing. Also, weather resistance tends to decrease, and the coefficient of thermal expansion tends to become too high.

[0039] CaO is a component that broadens the vitrification range and improves weather resistance. The CaO content is preferably 0-25%, 0-20%, 0-10%, and especially 0.1-3%. If the CaO content is too low, vitrification may become difficult. Also, the viscosity of the glass (softening point, etc.) may increase, making sealing at low temperatures difficult. On the other hand, if the CaO content is too high, the glass becomes thermally unstable, and devitrification is more likely to occur during melting or firing. Also, weather resistance tends to decrease, and the coefficient of thermal expansion tends to become too high.

[0040] SrO is a component that broadens the vitrification range and improves weather resistance. The SrO content is preferably 0-25%, 0-20%, 0-10%, and especially 0.1-3%. If the SrO content is too low, vitrification may become difficult. Also, the viscosity of the glass (softening point, etc.) may increase, making sealing at low temperatures difficult. On the other hand, if the SrO content is too high, the glass becomes thermally unstable, and it is more likely to devitrify during melting or firing. Also, weather resistance tends to decrease, and the coefficient of thermal expansion tends to become too high.

[0041] BaO is a component that broadens the vitrification range and improves weather resistance. The BaO content is preferably 0-25%, 0.1-20%, 0.5-10%, and especially 1-7%. If the BaO content is too low, vitrification may become difficult. Also, the viscosity of the glass (softening point, etc.) may increase, making sealing at low temperatures difficult. On the other hand, if the BaO content is too high, the glass becomes thermally unstable, and it is more likely to devitrify during melting or firing. Also, weather resistance tends to decrease, and the coefficient of thermal expansion tends to become too high.

[0042] ZnO is a component that broadens the vitrification range and improves weather resistance. The ZnO content is preferably 0-25%, 0.1-20%, 0.5-10%, and particularly preferably 1-7%. If the ZnO content is too low, vitrification becomes difficult. Also, the viscosity of the glass (softening point, etc.) increases, making low-temperature sealing difficult. On the other hand, if the ZnO content is too high, the glass becomes thermally unstable, and it is prone to devitrification during melting or firing. Also, weather resistance tends to decrease, and the coefficient of thermal expansion tends to become too high.

[0043] La ２ O ３ This is a component that thermally stabilizes glass and suppresses devitrification. ２ O ３ The content is preferably 0-10%, 0-5%, 0-2%, and particularly 0.1-1%. ２ O ３ If the content is too high, the viscosity (softening point, etc.) of the glass increases, making low-temperature sealing difficult.

[0044] AgI is a component that reduces the viscosity (softening point, etc.) of glass. The AgI content is preferably 0-3%, 0-2%, and especially 0-1%. If the AgI content is too high, the coefficient of thermal expansion tends to become too high.

[0045] B ２ O ３ This is a component that forms a glass network. ２ O ３ The content is preferably 0-20%, 0-10%, and particularly 0-5%. ２ O ３ If the content is too high, the viscosity (softening point, etc.) of the glass increases, making low-temperature sealing difficult, and the glass becomes more prone to phase separation. It also becomes more difficult to vitrify.

[0046] WO ３ It is a component that reduces the coefficient of thermal expansion. It is also a component that improves the water resistance of the sealing interface. WO ３ The content is preferably 0-20%, 0-10%, 0-5%, and especially 0-3%. ３ If the content is too high, the glass becomes thermally unstable, making it prone to devitrification during melting or firing, and increasing the viscosity (softening point, etc.) of the glass, making low-temperature sealing difficult.

[0047] P ２ O ５ This component forms a glass network and also thermally stabilizes the glass. ２ O ５ The content is preferably 0-10%, 0-5%, 0-2%, and especially 0-1%. ２ O ５ If the content is too high, the viscosity (softening point, etc.) of the glass increases, making low-temperature sealing difficult and reducing its weather resistance.

[0048] SiO ２ SiO is a component that thermally stabilizes glass and reduces its coefficient of thermal expansion. ２ The content is preferably 0-5%, 0-2%, and especially 0-1%. SiO ２If the content is too high, the viscosity (softening point, etc.) of the glass increases, making low-temperature sealing difficult.

[0049] TiO ２ This component thermally stabilizes the glass and reduces its coefficient of thermal expansion. It also improves the water resistance of the sealing interface. TiO ２ The content is preferably 0-5%, 0-2%, and especially 0-1%. ２ If the content is too high, the viscosity (softening point, etc.) of the glass increases, making low-temperature sealing difficult.

[0050] CEO ２ CeO is a component that thermally stabilizes glass and reduces its coefficient of thermal expansion. ２ The content is preferably 0-5%, 0-2%, and especially 0-1%. CeO ２ If the content is too high, the viscosity (softening point, etc.) of the glass increases, making low-temperature sealing difficult.

[0051] MnO is a component that thermally stabilizes glass and enhances its weather resistance. It also enhances its reactivity with the material to be sealed. The MnO content is preferably 0-5%, 0-2%, and especially 0-1%. If the MnO content is too high, the viscosity (softening point, etc.) of the glass increases, making low-temperature sealing difficult.

[0052] Cr ２ O ３ This component thermally stabilizes the glass and enhances its weather resistance. It also enhances its reactivity with the substrate. Cr ２ O ３ The content is preferably 0-5%, 0-2%, and especially 0-1%. Cr ２ O ３ If the content is too high, the viscosity (softening point, etc.) of the glass increases, making low-temperature sealing difficult.

[0053] Fe ２ O ３ This component thermally stabilizes the glass and enhances its weather resistance. It also enhances its reactivity with the substrate. Fe ２ O ３The content is preferably 0-5%, 0-2%, and especially 0-1%. Fe ２ O ３ If the content is too high, the viscosity (softening point, etc.) of the glass increases, making low-temperature sealing difficult.

[0054] Co ３ O ４ This component thermally stabilizes the glass and enhances its weather resistance. It also enhances its reactivity with the substrate. Co ３ O ４ The content is preferably 0-5%, 0-2%, and especially 0-1%. ３ O ４ If the content is too high, the viscosity (softening point, etc.) of the glass increases, making low-temperature sealing difficult.

[0055] NiO is a component that thermally stabilizes glass and enhances its weather resistance. It also enhances its reactivity with the material to be sealed. The NiO content is preferably 0-5%, 0-2%, and especially 0-1%. If the NiO content is too high, the viscosity (softening point, etc.) of the glass increases, making low-temperature sealing difficult.

[0056] Ga ２ O ３ This component thermally stabilizes the glass and enhances its weather resistance, but because it is very expensive, its content is preferably less than 0.1%.

[0057] Y ２ O ３ , GeO ２ Sb ２ O ３ These are components that thermally stabilize the glass and suppress devitrification, and each can be added in amounts of less than 5%. If the content of these components is too high, the glass becomes thermally unstable and is more prone to devitrification during melting or firing.

[0058] The sealing material of the present invention contains glass powder made from the above-mentioned glass composition. The sealing material of the present invention may also contain refractory filler powder to improve mechanical strength or adjust the coefficient of thermal expansion. The mixing ratio is preferably 40 to 100 volume% glass powder, 0 to 60 volume% refractory filler powder, 50 to 90 volume% glass powder, 10 to 50 volume% refractory filler powder, 55 to 80 volume% glass powder, 20 to 45 volume% refractory filler powder, and especially 60 to 70 volume% glass powder and 30 to 40 volume% refractory filler powder. If the content of refractory filler powder is too high, the proportion of glass powder becomes relatively low, making it difficult to ensure the desired fluidity.

[0059] The fire-resistant filler powder is Zr ２ WO ４ (PO ４ ) ２ It is preferable that it contains Zr. ２ WO ４ (PO ４ ) ２ This material has the property of being less reactive with the glass powder according to the present invention, and further significantly reducing the thermal expansion coefficient of the sealing material.

[0060] Furthermore, the sealing material of the present invention uses Zr as a fire-resistant filler powder. ２ WO ４ (PO ４ ) ２ Other fire-resistant filler powders can also be used. Other fire-resistant filler powders include NbZr(PO ４ ) ３ , Zr ２ MoO ４ (PO ４ ) ２ , Hf ２ WO ４ (PO ４ ) ２ , Hf ２ MoO ４ (PO ４ ) ２ Zirconium phosphate, zircon, zirconia, tin oxide, aluminum titanate, quartz, β-spodumene, mullite, titania, quartz glass, β-eucryptite, β-quartz, willemite, cordierite, Sr ０．５Zr ２ (PO ４ ) ３ Powders consisting of the above can be used individually or in combination of two or more types.

[0061] The refractory filler powder is preferably in a substantially spherical shape. This prevents the flowability of the glass powder from being hindered by the refractory filler powder when the glass powder softens, resulting in improved fluidity of the sealing material. It also makes it easier to obtain a smooth glaze layer. Furthermore, even if some of the refractory filler powder is exposed on the surface of the glaze layer, the stress in this area is distributed because the refractory filler powder is substantially spherical. As a result, when sealing, even if the object to be sealed comes into contact with the glaze layer, it is less likely to be subjected to undue stress on the object to be sealed, making it easier to ensure airtightness.

[0062] Average particle size D of fire-resistant filler powder ５０ The particle size is preferably 0.2 to 20 μm, and particularly preferably 2 to 15 μm. ５０ If the size is too large, the sealing layer tends to become thicker. On the other hand, the average particle size D ５０ If the particle size is too small, the refractory filler powder will dissolve into the glass during sealing, making the glass more prone to devitrification. ５０ This refers to a value measured on a volume basis, and specifically to a value measured by laser diffraction.

[0063] In the sealing material of the present invention, the softening point is preferably 360°C or lower, 355°C or lower, and particularly 350°C or lower. If the softening point is too high, the viscosity of the glass increases, which raises the sealing temperature and may degrade the element due to the heat during sealing. The lower limit of the softening point is not particularly limited, but in reality it is 180°C or higher. Here, "softening point" refers to the average particle diameter D ５０ This refers to the value measured using a macro-type differential thermal analyzer with sealing material of 0.5 to 20 μm thickness as the measurement sample. The measurement conditions are as follows: measurement starts from room temperature, and the heating rate is 10°C / min. The softening point measured by the macro-type differential thermal analyzer refers to the temperature (Ts) at the fourth inflection point in the measurement curve shown in Figure 1.

[0064] In the sealing material of the present invention, the coefficient of thermal expansion in the temperature range of 30 to 150°C is 20 × 10－７ / ℃~200×10 －７ / ℃, 30×10 －７ / ℃~160×10 －７ / ℃, 40×10 －７ / ℃~140×10 －７ / ℃, especially 50 × 10 －７ / ℃~120×10 －７ It is preferable that the coefficient of thermal expansion is / °C. If the coefficient of thermal expansion falls outside the above range, the difference in thermal expansion with the material to be sealed will make the sealed portion prone to damage during or after sealing.

[0065] Next, an example of a method for producing glass powder and sealing material according to the present invention, and a method for using them, will be described.

[0066] First, the raw material powder, which has been blended to achieve the desired glass composition, is melted at 700-1000°C for 1-2 hours until a homogeneous glass is obtained. Next, the obtained molten glass is formed into a film or the like, then crushed and classified to produce glass powder. The average particle size D of the glass powder is... ５０ The particle size is preferably about 1 to 20 μm. If necessary, various refractory filler powders are added to the glass powder and mixed to form a sealing material.

[0067] Next, a sealing material paste is prepared by adding a vehicle to the sealing material and kneading it. The vehicle mainly consists of an organic solvent and a resin, with the resin added to adjust the viscosity of the paste. Surfactants, thickeners, etc., may also be added as needed.

[0068] The organic solvent is preferably one that has a low boiling point (for example, a boiling point of 300°C or less), produces little residue after firing, and does not alter the glass, and its content is preferably 10 to 40% by mass. Preferred organic solvents include propylene carbonate, toluene, N,N'-dimethylformamide (DMF), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl carbonate, butylcarbitol acetate (BCA), isoamyl acetate, dimethyl sulfoxide, acetone, and methyl ethyl ketone. Furthermore, it is even more preferable to use a higher alcohol as the organic solvent. Because higher alcohols themselves are viscous, they can be pasteurized without adding resin to the vehicle. Also, pentanediol and its derivatives, specifically diethylpentanediol (C), are also preferred. ９ H ２０ O ２ ) also has excellent viscosity, so it can be used as a solvent.

[0069] The resin is preferably one that has a low decomposition temperature, produces little residue after firing, and does not easily alter the glass, and its content is preferably 0.1 to 20% by mass. It is preferable to use nitrocellulose, polyethylene glycol derivatives, polyethylene carbonate, acrylic acid esters (acrylic resins), etc., as the resin.

[0070] Next, the sealing material paste is applied to the sealing area of ​​the object to be sealed, which is made of metal, ceramic, or glass, using a dispenser or screen printing machine, dried, and then glazed at 280-320°C. After that, another object to be sealed is brought into contact with the paste and heat-treated at 300-400°C, causing the glass powder to soften and flow, thus sealing the two objects together.

[0071] The glass powder according to the present invention can be used for purposes other than sealing, such as coating and filling. Furthermore, it can be used in forms other than paste, specifically as powder, green sheet, or tablet (a powder material sintered into a predetermined shape).

[0072] The present invention will be described in detail based on the examples. Tables 1 and 2 show examples of the present invention (samples No. 1 to 7, 9 to 12) and comparative examples (samples No. 8, 13).

[0073]

[0074]

[0075] First, the raw material powders, prepared to match the glass composition shown in the table, were placed in a platinum crucible and melted in air at 700-1000°C for 1-2 hours. Then, the molten glass was formed into a film using a water-cooled roller, and the film was crushed in a ball mill. Finally, it was passed through a sieve with a mesh size of 75 μm to determine the average particle size D. ５０ This yielded glass powder with a particle size of approximately 10 μm.

[0076] Subsequently, as shown in the table, the obtained glass powder and refractory filler powder were mixed to obtain a mixed powder.

[0077] The fire-resistant filler powder contains approximately spherical Zr ２ WO ４ (PO ４ ) ２ (ZWP is indicated in the table) was used. Note that the average particle size D of the refractory filler powder was used. ５０ It was approximately 10 μm.

[0078] For samples No. 1 to 13, the glass transition temperature, thermal expansion coefficient, softening point, fluidity, weather resistance, and water resistance of the sealing interface were evaluated.

[0079] The glass transition temperature and the coefficient of thermal expansion in the temperature range of 30 to 150°C were evaluated as follows: First, the mixed powder was placed in a rod-shaped mold and press-molded. Then, it was fired on an alumina substrate coated with a release agent at 280 to 350°C for 10 minutes. After that, the fired body was processed into a predetermined shape and measured using a TMA device.

[0080] The softening point was measured using a macro-type differential thermal analyzer, with the fourth inflection point being defined as the softening point. The measurement environment was air, the heating rate was 10°C / min, and the measurement started from room temperature.

[0081] Fluidity was evaluated as follows: A mass equal to the combined density of the mixed powder was placed in a 20 mm diameter mold and pressed to obtain a compacted powder. The compacted powder was then fired on a glass substrate at 350°C for 10 minutes. A compacted powder with a flow diameter of 19 mm or more was marked with "○", and one with a flow diameter less than 19 mm was marked with "×".

[0082] Weather resistance was evaluated using an accelerated degradation test (PCT) conducted by PCT (Pressure Cooker Test). Specifically, the fired bodies prepared as described above were kept in an environment of 121°C, 2 atmospheres, and 100% relative humidity for 24 hours. After visual inspection, bodies without cracks were marked with a "○" and bodies with cracks were marked with a "×".

[0083] The water resistance of the sealing interface was evaluated by an accelerated degradation test using the PCT (Pressure Cooker Test). A mass equal to the combined density of the mixed powder was placed in a 10 mm diameter mold and press-molded to obtain a compacted powder. The compacted powder was then fired on a glass substrate at 350°C for 60 minutes. The fired bodies prepared above were held for 24 hours in an environment of 121°C, 2 atmospheres, and 100% relative humidity. Visual inspection determined that no deterioration had occurred at the interface between the fired body and the glass substrate, and "○" indicated deterioration.

[0084] As is clear from the table, samples No. 1-7 and 9-12 showed good evaluations of fluidity, weather resistance, and water resistance of the sealing interface. On the other hand, sample No. 8 showed Nb ２ O ５ and ZrO ２ Because it did not contain ZrO, it had poor weather resistance, and cracks formed in the fired body. In addition, alteration occurred at the sealing interface. Sample No. 13 was ZrO ２ Because it did not contain [specific ingredient], it had poor weather resistance, and cracks appeared in the fired body. In addition, deterioration occurred at the sealing interface.

[0085] The glass composition of the present invention is suitable for sealing quartz crystal oscillator packages, and is also suitable for sealing hermetic packages such as semiconductor integrated circuits, planar display devices, LED glass terminals, and aluminum nitride substrates. It can also be used as a sealing material for metals and vacuum-insulated glass.

Claims

The glass composition is, in mol%, TeO ２ 15-80%, MoO ３ 0.1-30%, V ２ O ５ 5-40%, Nb ２ O ５ 0.1-10%, ZrO ２ A glass composition characterized by containing 2.1 to 10%. 　 As a glass composition, in mol%, CuO 0.1 to 35%, Al ２ O ３ 0.1 to 10%, K ２ O 1 to 30%, PbO 0 to 10%, and substantially free of SeO ２ The glass composition according to claim 1, characterized in that it does not contain SeO. 　 As for the glass composition, in mol% Li ２ O + Na ２ It contains 0.1 to 15% of O, in molar ratio, (Li ２ O + Na ２ O) / K ２ The glass composition according to claim 1 or 2, characterized in that O is 0.05 to 1. 　 The glass composition according to claim 1 or 2, characterized in that it contains 0.1 to 20% of MgO + CaO + SrO + BaO + ZnO in mol% as the glass composition. 　 As for the glass composition, in mol% La ２ O ３ The glass composition according to claim 1 or 2, characterized by containing 0 to 10%. 　 A sealing material characterized by containing 40 to 100% by volume of glass powder made from the glass composition described in claim 1 or 2, and 0 to 60% by volume of refractory filler powder. 　 The sealing material according to claim 6, characterized in that the fire-resistant filler powder is substantially spherical. 　 All or part of the fire-resistant filler powder is Zr ２ WO ４ (PO ４ ) ２ The sealing material according to claim 6, characterized in that it is the same as the one described above. 　 The sealing material according to claim 6, characterized in that it is used in a quartz crystal oscillator package. The sealing material according to claim 6, characterized in that it is used for vacuum insulated glass. 　 A sealing material paste characterized by containing the sealing material and vehicle described in claim 6.

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