CN113574025A - Glass composition and sealing material - Google Patents
Glass composition and sealing material Download PDFInfo
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- CN113574025A CN113574025A CN202080021106.3A CN202080021106A CN113574025A CN 113574025 A CN113574025 A CN 113574025A CN 202080021106 A CN202080021106 A CN 202080021106A CN 113574025 A CN113574025 A CN 113574025A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1003—Pure inorganic mixtures
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/02—Inorganic compounds
- C09K2200/0217—Salts
- C09K2200/0234—Phosphorous-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/02—Inorganic compounds
- C09K2200/0239—Oxides, hydroxides, carbonates
Abstract
The invention provides a glass composition which does not contain lead harmful to the environment and can be sealed at low temperature and a sealing material using the glass composition. The glass composition is characterized by comprising, in mol%: li2O+K2O 1～30％、TeO2 30～80％、MoO3 5～30％。
Description
Technical Field
The present invention relates to a glass composition which does not contain harmful lead and can be hermetically sealed at a low temperature, and a sealing material using the glass composition.
Background
Sealing materials are used for semiconductor integrated circuits, crystal oscillators, flat panel display devices, glass terminals for LDs, and the like.
Since the above sealing material requires chemical durability and heat resistance, a glass sealing material is used instead of a resin adhesive. The sealing material is further required to have properties such as mechanical strength, fluidity, and weather resistance, but in sealing of electronic components having a heat-labile element, it is required to reduce the sealing temperature as much as possible. Specifically, sealing at a temperature of less than 450 ℃ is required. Therefore, as a glass satisfying the above characteristics, a lead borate glass containing a large amount of PbO having a great melting point lowering effect is widely used (for example, see patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 63-315536
Patent document 2: japanese laid-open patent publication No. 6-24797
Disclosure of Invention
Technical problem to be solved by the invention
In recent years, environmental problems have been pointed out with respect to PbO contained in lead borate glasses, and it has been desired to replace lead borate glasses with glasses that do not contain PbO. Therefore, various low-melting point glasses have been developed as substitutes for the lead-boric acid glass. Among them, Bi described in patent document 22O3-B2O3The glass is expected as an alternative candidate to the lead-boric acid glass, but the sealing temperature is as high as 450 ℃ or higher, and the glass cannot be used for applications requiring sealing at lower temperatures.
In view of the above circumstances, an object of the present invention is to provide a glass composition which does not contain lead harmful to the environment and can perform sealing at a low temperature, and a sealing material using the same.
Means for solving the problems
The glass composition of the present invention is characterized by containing, in mol%: li2O+K2O1～30％、TeO230～80％、MoO35 to 30 percent. Here, "Li2O+K2O "means Li2O and K2The total amount of O.
The glass composition of the present invention is obtained by reacting Li2O and K2The total amount of O is 1% or more, thereby achieving a low softening point. In general, when the melting point of the glass is lowered, the glass tends not to be vitrified or to cause phase separation, and it is difficult to obtain a homogeneous glass2The content of (A) is defined as 30% or more, MoO3Since the content of (b) is 5% or more, the glass is stable and homogeneous glass can be obtained.
The glass composition of the present invention is characterized by containing, in mol%: li2O+Na2O+K2O 1～30％、TeO230～80％、MoO35 to 30 percent. Here, "Li2O+Na2O+K2O "means Li2O、Na2O and K2The total amount of O.
The glass composition of the present invention preferably contains, in mol%: li2O 1～30％。
In the glass composition of the present invention, preferably, Li is present in a molar ratio2O/K2O is 0.3 to 5. Here, "Li2O/K2O' means that Li is substituted by2O content divided by K2The content of O.
The glass composition of the present invention preferably further contains, in mol%: TiO 22+Al2O30 to 10 percent. Here, "TiO2+Al2O3"means TiO2And Al2O3The total amount of (a).
The glass composition of the present invention preferably further contains, in mol%: CuO 0-30%, WO30～20％、P2O50～10％。
The sealing material of the present invention is characterized by containing: 40 to 100 vol% of a glass powder containing the glass composition; and 0-60 vol% of a refractory filler powder.
In the sealing material of the present invention, the refractory filler powder is preferably substantially spherical.
In the sealant of the present invention, the refractory filler powder preferably contains Zr2WO4(PO4)2。
The sealing material of the present invention is preferably used for crystal oscillator applications.
The sealing material paste of the present invention is characterized by containing: the above sealing material; and a carrier.
Effects of the invention
A glass composition which does not contain lead harmful to the environment and can be sealed at a low temperature, and a sealing material using the glass composition can be provided.
Drawings
Fig. 1 is a schematic view showing a measurement curve obtained by a macroscopic differential thermal analyzer.
Detailed Description
The glass composition of the present invention preferably contains Li in mol%2O+K2O 1～30％、TeO230～80％、MoO35 to 30 percent. In addition, the glass composition of the present invention preferably contains Li in mol%2O+Na2O+K2O 1～30％、TeO230～80％、MoO35 to 30 percent. The reason why the glass composition is limited to the above is shown below. In the following description of the content of each component, "%" means "% by mole" unless otherwise specified.
Li2O and K2O is a component that lowers the viscosity (softening point, etc.) of the glass. Li2O+K2O is preferably 1 to 30%, 2 to 30%, 5 to 28%, particularly preferably 7 to 26%. If Li2O+K2When O is too small, the viscosity (softening point, etc.) of the glass increasesLow temperature sealing becomes difficult, and the glass becomes thermally unstable, and the glass easily devitrifies when melted or fired. On the other hand, if Li2O+K2When O is too large, the glass becomes thermally unstable and the glass is liable to devitrify during melting or firing.
In terms of molar ratio, Li2O/K2O is preferably 0.3 to 5, 0.5 to 4, 0.7 to 3, and particularly preferably 0.8 to 2. If Li2O/K2When O is too small, the viscosity (softening point, etc.) of the glass increases, so that low-temperature sealing becomes difficult, and the glass becomes thermally unstable, so that the glass is likely to devitrify during melting or firing. On the other hand, if Li2O/K2When O is too large, the glass becomes thermally unstable, and the glass is likely to devitrify during melting or firing.
Na2O is also reacted with Li2O and K2O is a component that similarly lowers the viscosity (softening point, etc.) of the glass. Li2O+Na2O+K2O is preferably 1 to 30%, 2 to 30%, 5 to 28%, particularly preferably 7 to 26%. If Li2O+Na2O+K2When the amount of O is too small, the viscosity (softening point, etc.) of the glass increases, so that low-temperature sealing becomes difficult, and the glass becomes thermally unstable, so that the glass is likely to devitrify during melting or firing. On the other hand, if Li2O+Na2O+K2When O is too large, the glass becomes thermally unstable and the glass is liable to devitrify during melting or firing.
In addition, Li2O、Na2O and K2Preferable ranges of the content of O are as follows.
With Na2O and K2In comparison with O, Li2O is not likely to enhance devitrification of the glass and is likely to lower viscosity (softening point, etc.) of the glass, and Li is preferred2O to Na2O and K2O is much. In particular, Li2The preferable content of O is 1-30%, 2-25%, 3-20%, especially preferable content is 5-18%, Na2The content of O is preferably 0 to 20%, 1 to 15%, 2 to 14%, particularly preferably 3 to 13%, K2The content of O is preferably 0 to 20%, 1 to 15%, 2 to 14%, and particularly preferably 3 to 13%.
TeO2Is an ingredient that forms a glass network and improves weatherability. TeO2The content of (b) is 30 to 80%, preferably 40 to 70%, and particularly preferably 50 to 65%. If TeO2When the content of (b) is too small, the glass becomes thermally unstable, and the glass is liable to devitrify during melting or firing, and the weather resistance is liable to deteriorate. On the other hand, if TeO2When the content (c) is too large, the viscosity (softening point, etc.) of the glass becomes high, low-temperature sealing becomes difficult, and the glass becomes thermally unstable and is liable to devitrify during melting or firing. Further, the thermal expansion coefficient of the glass tends to be too high.
MoO3Is an ingredient that forms a glass network and improves weatherability. MoO3The content of (b) is 5 to 30%, preferably 7 to 27%, and particularly preferably 10 to 25%. If MoO3When the content of (b) is too small, the glass becomes thermally unstable, the glass is likely to devitrify during melting or firing, and the viscosity (softening point and the like) of the glass becomes high, so that low-temperature sealing is difficult. On the other hand, if MoO3When the content (b) is too large, the glass becomes thermally unstable, the glass is easily devitrified during melting or firing, and the thermal expansion coefficient of the glass tends to be too high.
The glass composition of the present invention may contain the following components in addition to the above components in the glass composition.
TiO2And Al2O3Is a component for improving weather resistance. TiO 22+Al2O3Preferably 0 to 10%, 0.1 to 8%, and particularly preferably 1 to 6%. TiO 22+Al2O3If the amount is too large, the viscosity (softening point, etc.) of the glass increases, so that low-temperature sealing becomes difficult, and the glass becomes thermally unstable, so that the glass is likely to devitrify during melting or firing.
In addition, TiO2And Al2O3The preferable range of the content of (b) is as follows.
TiO2The preferred content is 0-8%, 0.1-6%, 1-5%, Al2O3The content is preferably 0 to 5%, 0 to 3%, 0.1 to 2%.
CuO is a component that lowers the viscosity (softening point, etc.) of the glass and lowers the thermal expansion coefficient of the glass. The content of CuO is preferably 0 to 30%, 0 to 10%, 0 to 6%, and particularly preferably 0.1 to 2%. If the content of CuO is too large, the glass becomes thermally unstable, and the glass is likely to devitrify during melting or firing.
WO3Is a component that lowers the coefficient of thermal expansion of the glass. WO3The content of (b) is preferably 0 to 20%, 0 to 10%, and particularly preferably 0.1 to 5%. If WO3When the content of (b) is too large, the glass becomes thermally unstable, and the glass is likely to devitrify during melting or firing, and the viscosity (softening point, etc.) of the glass becomes high, and low-temperature sealing becomes difficult.
P2O5Is a component that forms a network of glass and thermally stabilizes the glass. P2O5The content is preferably 0 to 10%, 0 to 5%, 0 to 2%, particularly preferably 0.1 to 1%. If P2O5When the content (c) is too large, the viscosity (softening point, etc.) of the glass increases, low-temperature sealing becomes difficult, and weather resistance tends to decrease.
Ag2O is a component that lowers the viscosity (softening point, etc.) of the glass. Ag2The content of O is preferably 0 to 10%, 0 to 5%, and particularly preferably 0 to 2%. If Ag2When the content of O is too large, the glass becomes thermally unstable and the glass is liable to devitrify during melting or firing.
AgI is a component that reduces the viscosity (softening point, etc.) of glass. The content of AgI is preferably 0 to 10%, 0 to 5%, and particularly preferably 0 to 2%. If the content of AgI is too large, the thermal expansion coefficient of the glass tends to be too high.
MgO, CaO, SrO and BaO have the effect of thermally stabilizing the glass and improving the weather resistance, and the content thereof is preferably 0 to 20% by weight, particularly preferably 0 to 10% by weight in total. If the total amount of MgO, CaO, SrO and BaO is too large, the glass becomes thermally unstable and is likely to devitrify during melting or firing. The contents of MgO, CaO, SrO and BaO are preferably 0 to 10%, particularly preferably 0 to 5%, respectively.
ZnO is a component that reduces the viscosity (softening point, etc.) of glass and improves weather resistance. The content of ZnO is preferably 0 to 10%, and particularly preferably 0 to 5%. If the content of ZnO is too large, the glass becomes thermally unstable and the glass is liable to devitrify during melting or firing.
Nb2O5Is a component that thermally stabilizes the glass and improves the weatherability. Nb2O5The content of (b) is preferably 0 to 10%, particularly preferably 0 to 5%. If Nb2O5When the content (c) is too large, the viscosity (softening point, etc.) of the glass increases, and low-temperature sealing becomes difficult.
V2O5Is a component that forms a glass network and reduces the viscosity (softening point, etc.) of the glass. V2O5The content is preferably 0 to 10%, particularly preferably 0 to 5%. If V2O5When the content of (b) is too large, the glass becomes thermally unstable, the glass is liable to devitrify during melting or firing, and the weather resistance is liable to decrease.
Ga2O3Is a component for thermally stabilizing glass and improving weather resistance, but since it is very expensive, its content is preferably less than 0.01%, and particularly preferably it does not contain Ga2O3。
SiO2、GeO2、Fe2O3、NiO、CeO2、B2O3、Sb2O3、ZrO2The components are components for thermally stabilizing the glass and inhibiting devitrification, and may be added up to 2% or less, respectively. If the content of these is too large, the glass becomes thermally unstable and the glass is liable to devitrify during melting or firing.
For environmental reasons, the glass composition of the present invention preferably contains substantially no PbO. Here, "PbO is not substantially contained" means that the content of PbO in the glass composition is 1000ppm or less.
The sealing material of the present invention contains a glass powder containing the above glass composition. The sealing material of the present invention may contain a refractory filler powder in order to improve mechanical strength or adjust a thermal expansion coefficient. The mixing ratio of the glass powder to the fire-resistant filler powder is 40-100 vol% and 0-60 vol% of the fire-resistant filler powder, preferably 50-99 vol% of the glass powder and 1-50 vol% of the fire-resistant filler powder, particularly 60-95 vol% of the glass powder and 5-40 vol% of the fire-resistant filler powder. If the content of the refractory filler powder is too large, the ratio of the glass powder is relatively small, and it is difficult to secure desired fluidity.
The refractory filler powder is preferably substantially spherical. In this case, when the glass powder is softened, the flowability of the glass powder is not easily inhibited by the refractory filler powder, and as a result, the flowability of the sealing material is improved. In addition, a smooth glaze layer is easily obtained. Further, even if a part of the refractory filler powder is exposed on the surface of the glaze layer, since the refractory filler powder is substantially spherical, stress is dispersed in the part, and further, even if the object to be sealed is brought into contact with the glaze layer at the time of sealing, it is difficult to apply an improper stress to the object to be sealed, and as a result, airtightness is easily ensured. The "substantially spherical shape" in the present invention is not limited to a spherical shape, but in the refractory filler powder, the value obtained by dividing the shortest diameter passing through the center of gravity of the refractory filler powder by the longest diameter is 0.5 or more, preferably 0.7 or more.
The refractory filler powder preferably contains Zr2WO4(PO4)2。Zr2WO4(PO4)2The glass powder is less likely to react with the glass powder, and the coefficient of thermal expansion of the sealing material can be effectively reduced.
In addition, Zr may be used as the sealing material of the present invention2WO4(PO4)2Other refractory filler powder is used as the refractory filler powder. As another refractory filler powder, a powder containing NbZr (PO) may be used4)3、Zr2MoO4(PO4)2、Hf2WO4(PO4)2、Hf2MoO4(PO4)2Zirconium phosphate, zircon, zirconia, tin oxide, aluminum titanate, quartz, beta-spodumene, mullite, titania, quartz glass, beta-eucryptite, beta-quartz, willemite, cordierite, Sr0.5Zr2(PO4)3Etc. can be used alone or in combination of two or more. The particle diameter of the refractory filler powder is preferably the average particle diameter D50About 0.2 to 20 μm.
The softening point of the sealing material of the present invention is preferably 380 ℃ or lower, 370 ℃ or lower, 360 ℃ or lower, and particularly preferably 350 ℃ or lower. If the softening point is too high, the viscosity of the glass increases, and therefore the sealing temperature increases, which may deteriorate the element during sealing. The lower limit of the softening point is not particularly limited, but is actually 180 ℃ or higher. Here, "softening point" means the average particle diameter D50A value measured by a macroscopic differential thermal analyzer using a sealing material of 0.5 to 20 μm as a measurement sample. As the measurement conditions, the temperature was measured from room temperature, and the rate of temperature rise was 10 ℃/min. The softening point measured by the macro-type differential thermal analyzer is a temperature (Ts) at the fourth bending point in the measurement curve shown in fig. 1.
The sealing material of the present invention preferably has a thermal expansion coefficient (30 to 150 ℃) of 20X 10-7/℃～200×10-7/℃、30×10-7/℃～160×10-7Per DEG C, particularly preferably 40X 10-7/℃～140×10-7V. C. The thermal expansion coefficient is too low or too high, and the sealing portion is easily broken at the time of sealing or after sealing due to the difference in expansion between the sealing material and the material to be sealed.
The sealing material of the present invention having the above characteristics is particularly suitable for crystal oscillator applications requiring sealing at low temperatures.
Next, an example of a method for producing a glass powder using the glass composition of the present invention and a method for using the glass composition of the present invention as a sealing material will be described.
Firstly, the raw material powder prepared into the composition is melted at the temperature of 800-1000 ℃ for 1-2 hours until homogeneous glass is obtained. Next, the molten glass is formed into a film or the like, and then pulverized and classified to produce a glass powder containing the glass composition of the present invention. The average particle diameter D of the glass powder50Preferably about 2 to 20 μm. If necessary, various refractory fillers are added to the glass powderSealing material of powder.
Next, a carrier is added to the glass powder (or the sealing material) and kneaded to prepare a glass paste (or a sealing material paste). The carrier preferably mainly contains an organic solvent and a resin, and the resin is added for the purpose of adjusting the viscosity of the paste. Further, a surfactant, a thickener, or the like may be added as necessary.
The organic solvent is preferably an organic solvent that does not change the glass in quality, except that the organic solvent has a low boiling point (for example, a boiling point of 300 ℃ or less) and that the residue after firing is small, and the content thereof is preferably 10 to 40% by mass. As the organic solvent, propylene carbonate, toluene, N' -Dimethylformamide (DMF), 1, 3-dimethyl-2-imidazolidinone (DMI), dimethyl carbonate, Butyl Carbitol Acetate (BCA), isoamyl acetate, dimethyl sulfoxide, acetone, methyl ethyl ketone, or the like is preferably used. In addition, as the organic solvent, higher alcohols are more preferably used. The higher alcohol itself has viscosity, and thus can be gelatinized without adding a resin to the carrier. Furthermore, pentanediol and a derivative thereof, specifically, diethylpentanediol (C)9H20O2) Is also excellent in viscosity and therefore can be used for a solvent.
The resin is preferably one which has a low decomposition temperature, a small amount of residue after firing, and hardly causes glass deterioration, and the content thereof is preferably 0.1 to 20% by mass. As the resin, nitrocellulose, polyethylene glycol derivatives, polyethylene carbonate, acrylic esters (acrylic resins), and the like are preferably used.
Next, a paste is applied to a sealed portion between a first member made of metal, ceramic, or glass and a second member made of metal, ceramic, or glass using a dispenser such as a dispenser or a screen printer, dried, and heat-treated at a temperature of 300 to 440 ℃. By this heat treatment, the glass powder softens and flows, and the first member and the second member are sealed.
The glass composition of the present invention can be used for the purpose of coating, filling, etc., in addition to sealing applications. The resin composition may be used in a form other than paste, specifically, in the form of powder, green sheet, tablet, or the like.
Examples
The present invention will be described in detail based on examples. Tables 1 and 2 show examples (sample Nos. 1 to 12) and comparative examples (sample Nos. 13 and 14) of the present invention.
[ Table 1]
[ Table 2]
First, glass raw materials such as various oxides and carbonates are prepared so as to have glass compositions shown in the table, a glass batch is prepared, and then the glass batch is placed in a platinum crucible and melted at a temperature of 800 to 1000 ℃ for 1 to 2 hours. Next, a part of the molten glass was poured into a stainless steel mold as a sample for TMA (push rod thermal expansion coefficient measurement), and the other molten glass was formed into a film shape by a water-cooled roll. Sample TMA was obtained by subjecting sample No.2 containing no refractory filler powder to a predetermined slow cooling treatment (annealing) after molding. Finally, the film-like glass was pulverized by a ball mill and passed through a sieve having a pore diameter of 75 μm to obtain an average particle diameter D50About 10 μm glass powder.
Then, as shown in the table, samples nos. 1 and 3 to 13 in which the refractory filler powder was mixed were mixed with the obtained glass powder to obtain mixed powder.
As the refractory filler powder, substantially spherical Zr was used2WO4(PO4)2(ZWP in the table), NbZr (PO)4)3(noted as NZP in the table). The refractory filler powder has an average particle diameter D50About 10 μm.
The obtained mixed powder was fired at a temperature of 380 ℃ for 10 minutes to obtain a fired body. The obtained fired body was used as a sample for TMA.
The samples Nos. 1 to 12 were evaluated for glass transition temperature, thermal expansion coefficient, softening point and fluidity.
A sample for TMA was measured for its glass transition temperature and thermal expansion coefficient (30 to 150 ℃ C.) by using a TMA apparatus.
The softening point was measured by a macroscopic differential thermal analyzer. The measurement was carried out in an atmosphere at a temperature rise rate of 10 ℃ per minute from room temperature.
The fluidity was evaluated as follows. A5 g sample of the powder was placed in a mold having a diameter of 20mm and press-molded, and then fired on a glass substrate at a temperature of 380 ℃ for 10 minutes. The flow diameter of the fired body was 19mm or more and indicated as "O", and the flow diameter of the fired body was less than 19mm and indicated as "X".
As is clear from the table, samples Nos. 1 to 12, which are examples of the present invention, are excellent in fluidity. On the other hand, the sample No.13 as a comparative example contained excessive K2O, and TeO2Because of a small content of (b), devitrification occurs during firing. Sample No.14 contained excess MoO3And TeO2Is small and therefore is not vitrified.
Industrial applicability
The glass composition and the sealing material of the present invention are suitable for sealing a semiconductor integrated circuit, a crystal oscillator, a flat panel display device, a glass terminal for an LD, and an aluminum nitride substrate.
Claims (11)
1. A glass composition characterized by having a glass composition,
the glass composition contains, in mole%: li2O+K2O 1～30％、TeO230～80％、MoO3 5～30％。
2. A glass composition characterized by having a glass composition,
the glass composition contains, in mole%: li2O+Na2O+K2O 1～30％、TeO230～80％、MoO3 5～30％。
3. The glass composition according to claim 1 or 2,
the glass composition contains, in mole%: li2O 1～30％。
4. The glass composition according to any one of claims 1 to 3,
in terms of molar ratio, Li2O/K2O is 0.3 to 5.
5. The glass composition according to any one of claims 1 to 4,
the glass composition further comprises, in mole%: TiO 22+Al2O3 0～10％。
6. The glass composition according to any one of claims 1 to 5,
the glass composition further comprises, in mole%: 0-30% of CuO and WO3 0～20％、P2O5 0～10％。
7. A sealing material characterized in that it comprises, in a solid state,
the sealing material contains: 0 to 60 vol% of a refractory filler powder; and 40 to 100 vol% of a glass powder comprising the glass composition according to any one of claims 1 to 6.
8. The sealing material according to claim 7,
the refractory filler powder is substantially spherical.
9. Sealing material according to claim 7 or 8,
the refractory filler powder contains Zr2WO4(PO4)2。
10. Sealing material according to any of claims 7 to 9,
the sealing material is used for crystal oscillator applications.
11. A sealing material paste characterized in that,
the sealing material paste contains: the sealing material of any one of claims 7 to 10; and a carrier.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-118107 | 2019-06-26 | ||
| JP2019118107 | 2019-06-26 | ||
| JP2019148860A JP7385169B2 (en) | 2019-06-26 | 2019-08-14 | Glass compositions and sealing materials |
| JP2019-148860 | 2019-08-14 | ||
| PCT/JP2020/023577 WO2020262109A1 (en) | 2019-06-26 | 2020-06-16 | Glass composition and sealing material |
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| CN113574025A true CN113574025A (en) | 2021-10-29 |
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| CN202080021106.3A Pending CN113574025A (en) | 2019-06-26 | 2020-06-16 | Glass composition and sealing material |
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| CN (1) | CN113574025A (en) |
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| WO2022154034A1 (en) | 2021-01-14 | 2022-07-21 | 藤森工業株式会社 | Multilayer body and packaging bag |
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| JP6816538B2 (en) | 2017-01-31 | 2021-01-20 | 日本電気硝子株式会社 | Silver phosphoric acid-based glass composition and sealing material |
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| JP7385169B2 (en) | 2023-11-22 |
| JP2021004164A (en) | 2021-01-14 |
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