阅读说明：本技术 玻璃组合物以及密封材料 (Glass composition and sealing material ) 是由 山口贵久 于 2019-09-13 设计创作，主要内容包括：提供一种不含有对环境有害的铅且能够在低温下进行密封的玻璃组合物以及使用该玻璃组合物的密封材料。所述玻璃组合物的特征在于,以摩尔％计含有1～35％的K-2O、10～60％的TeO-2以及10～60％的MoO-3。(Provided are 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. The glass composition is characterized by containing 1-35% of K in mol% 2 O、10-60% of TeO 2 And 10-60% MoO 3 。)

1. A glass composition characterized by having a glass composition,

the glass composition contains 1-35% of K by mol%₂O, 10-60% of TeO₂And 10-60% MoO₃。

2. The glass composition according to claim 1,

the glass composition further contains 0-20% of Na in mol%₂O, 0-30% of CuO, and 0-25% of WO₃0 to 10% of TiO₂0 to 20% of Ag₂O and 0-10% AgI.

3. The glass composition according to claim 1 or 2,

the glass composition further contains 0-5% of P in mol%₂O₅。

4. 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 3.

5. The sealing material according to claim 4,

the sealing material is used for crystal oscillator applications.

6. A sealing material paste characterized in that,

the sealing material paste contains: the sealing material of claim 4 or 5; and a carrier.

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 same.

Background

Sealing materials are used for semiconductor integrated circuits, crystal oscillators, flat panel display devices, glass terminals for LDs, and the like.

Since chemical durability and heat resistance are required for the sealing material, a glass-based sealing material is used instead of a resin-based adhesive. The sealing material is also required to have properties such as mechanical strength, fluidity, and weather resistance, but it is required to keep the sealing temperature as low as possible for sealing an electronic component mounting a heat-labile component. In particular, sealing at less than 450 ℃ is required. Therefore, as a glass satisfying the above characteristics, a lead borate based 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 glass, and it has been desired to replace lead borate glass with glass containing no PbO. Therefore, various low-melting point glasses have been developed as substitutes for lead borate based glasses. Among them, Bi described in patent document 2₂O₃-B₂O₃Matrix glass is expected as an alternative to lead borate matrix glass, but the sealing temperature is as high as 450 ℃ or higher, and it cannot be used for applications requiring sealing at lower temperatures.

In view of the above, 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 glass composition.

Means for solving the problems

The glass composition of the present invention is characterized by containing 1 to 35% by mol of K₂O, 10-60% of TeO₂And 10-60% MoO₃。

The glass composition of the present invention is obtained by containing K in an amount of 1% or more₂O, thereby achieving a low softening point. Generally, when the melting point of the glass is lowered, the glass tends not to be vitrified or phase separation occurs, and it is difficult to obtain a uniform glass₂The content of (A) is defined to be 10% or more, MoO₃The content of (b) is specified to be 10% or more, so that the glass is stabilized and a uniform glass can be obtained.

The glass composition of the present invention preferably further contains 0 to 20 mol% of Na₂O, 0-30% of CuO, and 0-25% of WO₃0 to 10% of TiO₂0 to 20% of Ag₂O and 0-10% AgI.

The glass composition of the present invention preferably further contains 0 to 5% by mol of P₂O₅。

The sealing material of the present invention is characterized by containing: 0 to 60 vol% of a refractory filler powder; and 40 to 100 vol% of a glass powder containing the above glass composition.

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 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 diagram showing a measurement curve obtained by a macro-type differential thermal analyzer.

Detailed Description

The glass composition of the present invention contains 1 to 35 mol% of K₂O, 10-60% of TeO₂And 10-60% MoO₃. The reason why the glass composition is defined as described above is shown below. In the following description relating to the content of each component, "%" means "% by mole" unless otherwise specified.

K₂O is a component for lowering the viscosity (softening point, etc.) of the glass and lowering the thermal expansion coefficient of the glass. K₂The content of O is 1 to 35%, preferably 2 to 30%, 4 to 25%, and particularly preferably 5 to 20%. If K₂When the content of O is too small, the viscosity (softening point, etc.) of the glass becomes high, low-temperature sealing becomes difficult, and the glass becomes thermally unstable and is easily devitrified during melting or sintering. In addition, the thermal expansion coefficient of glass tends to become excessively high. On the other hand, if K₂When the content of O is too large, the glass becomes thermally unstable and is liable to devitrify during melting or sintering.

TeO₂Is an ingredient that forms a glass network and improves weatherability. TeO₂The content of (b) is 10 to 60%, preferably 15 to 60%, and particularly preferably 25 to 55%. If TeO₂When the content of (b) is too small, the glass becomes thermally unstable, and the glass is liable to devitrify during melting or sintering, 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 increases, so that low-temperature sealing becomes difficult, and the glass becomes thermally unstable, so that the glass is easily devitrified during melting or sintering. In addition, the thermal expansion coefficient of glass tends to become excessively high.

MoO₃Is an ingredient that forms a glass network and improves weatherability. MoO₃The content of (b) is 10 to 60%, preferably 15 to 55%, and particularly preferably 20 to 50%. If MoO₃When the content of (b) is too small, the glass becomes thermally unstable, and the glass is easily devitrified during melting or sintering, and the viscosity (softening point and the like) of the glass becomes high, and low-temperature sealing becomes difficult. On the other hand, if MoO₃Too much content of (B) causes the glass to become thermally unstable,glass is easily devitrified at the time of melting or sintering, and the thermal expansion coefficient of glass tends to become excessively high.

The glass composition of the present invention may contain the following components in addition to the above components in the glass component.

Na₂O is a component for lowering the viscosity (softening point, etc.) of the glass. Na (Na)₂The content of O is preferably 0 to 20%, 0 to 10%, and particularly preferably 0.1 to 5%. If Na₂When the content of O is too large, the glass becomes thermally unstable, and the glass is likely to devitrify during melting or sintering, and the weather resistance is likely to decrease.

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 sintering.

WO₃Is a component for lowering the thermal expansion coefficient of the glass. WO₃The content of (b) is preferably 0 to 25%, 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 easily devitrified during melting or sintering, and the viscosity (softening point, etc.) of the glass becomes high, and low-temperature sealing becomes difficult.

TiO₂Is a component for lowering the thermal expansion coefficient of the glass. TiO 2₂The content of (b) is preferably 0 to 10%, 0 to 6%, and particularly preferably 0.1 to 2%. If TiO₂When the content (c) is too large, the viscosity (softening point, etc.) of the glass increases, and low-temperature sealing becomes difficult.

Ag₂O is a component for lowering the viscosity (softening point, etc.) of the glass. Ag₂The content of O is preferably 0 to 20%, 0 to 10%, and particularly preferably 0.1 to 5%. If Ag₂When the content of O is too large, the glass becomes thermally unstable and is liable to devitrify during melting or sintering.

AgI is a component that reduces the viscosity (softening point, etc.) of the glass. The content of AgI is preferably 0 to 10%, 0 to 5%, and particularly preferably 0.1 to 2%. If the content of AgI is too large, the thermal expansion coefficient of the glass tends to become excessively high.

P₂O₅Is a component that forms a glass network and thermally stabilizes the glass. P₂O₅The content of (b) is preferably 0 to 5%, 0 to 2%, and 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.

Li₂O is a component for lowering the viscosity (softening point, etc.) of the glass. Li₂The content of O is preferably 0 to 20%, 0 to 10%, and particularly preferably 0 to 1%. If Li₂When the content of O is too large, the glass becomes thermally unstable, and the glass is likely to devitrify during melting or sintering, and the weather resistance is likely to decrease.

MgO, CaO, SrO and BaO have an 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 easily devitrified during melting or sintering. The contents of MgO, CaO, SrO and BaO are preferably 0 to 10%, particularly preferably 0 to 5%, respectively.

ZnO is a component for reducing the viscosity (softening point, etc.) of glass and improving 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 likely to devitrify during melting or sintering.

Nb₂O₅Is a component for thermally stabilizing glass and improving weather resistance. 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 becomes high, and low-temperature sealing tends to be difficult.

V₂O₅Is a component that forms a glass network and reduces the viscosity (softening point, etc.) of the glass. V₂O₅The content of (b) is preferably 0 to 10%, particularly preferably 0 to 5%. If V₂O₅When the content of (b) is too large, the glass becomes thermally unstable, and the glass is likely to devitrify during melting or sintering, and the weather resistance is likely to decrease.

Ga₂O₃Is a component for thermally stabilizing glass and improving weather resistance, but is very expensive, and therefore its content is preferably less than 0.01%, and particularly preferably it does not contain Ga₂O₃。

SiO₂、Al₂O₃、GeO₂、Fe₂O₃、NiO、CeO₂、B₂O₃、Sb₂O₃、ZrO₂Are components that thermally stabilize glass and inhibit devitrification, and can each be added to less than 2%. If the content of these is too large, the glass becomes thermally unstable and the glass is liable to devitrify during melting or sintering.

For environmental reasons, the glass composition of the present invention is preferably substantially free of PbO. Here, "substantially free of PbO" means that the content of PbO in the glass component 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 for the purpose of improving mechanical strength or adjusting the thermal expansion coefficient. The mixing ratio is preferably 40 to 100% by volume of the glass powder, 0 to 60% by volume of the fire-resistant filler powder, 50 to 99% by volume of the glass powder, 1 to 50% by volume of the fire-resistant filler powder, and particularly preferably 60 to 95% by volume of the glass powder and 5 to 40% by volume of the fire-resistant filler powder. If the content of the refractory filler is too large, the ratio of the glass powder becomes relatively small, and it becomes difficult to secure desired fluidity.

The refractory filler powder is not particularly limited, and various materials can be selected, but a material which is not easily reacted with the above glass powder is preferable.

Specifically, as the refractory filler, the following materials can be used alone or in combination of two or more: NbZr (PO)₄)₃、Zr₂WO₄(PO₄)₂、Zr₂MoO₄(PO₄)₂、Hf₂WO₄(PO₄)₂、Hf₂MoO₄(PO₄)₂Zirconium phosphate, zirconium phosphateStone, zirconia, tin oxide, aluminum titanate, quartz, beta-spodumene, mullite, titania, quartz glass, beta-eucryptite, beta-quartz, willemite, cordierite, Sr_0.5Zr₂(PO₄)₃Iso NaZr₂(PO₄)₃Type solid solutions, and the like. Further, the average particle diameter D is preferably used as the particle diameter of the refractory filler₅₀The particle size is about 0.2 to 20 μm.

The softening point of the glass composition and the sealing material of the present invention is preferably 400 ℃ or lower, 390 ℃ or lower, 380 ℃ or lower, and particularly preferably 370 ℃ 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, and it is considered that the lower limit is 180 ℃. Here, the term "softening point" means the average particle diameter D₅₀The glass composition and the sealing material having a thickness of 0.5 to 20 μm are measured as measurement samples by a macro-type differential thermal analyzer. 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 a macro-type differential thermal analyzer is the temperature (Ts) of the fourth bending point in the measurement curve shown in fig. 1.

The glass composition and the sealing material of the present invention preferably have 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. If the coefficient of thermal expansion is too low or too high, the sealing portion is likely to be broken during or after sealing due to a difference in expansion between the sealing portion and the material to be sealed.

The glass composition and the sealing material of the present invention having the above characteristics are particularly suitable for crystal oscillator applications requiring sealing at low temperature.

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, raw material powder prepared into the components is melted for 1 to 2 hours at 800 to 1000 DEG CUntil a homogeneous glass is obtained. Next, the molten glass is formed into a film or the like, and then pulverized and classified, thereby producing a glass powder containing the glass composition of the present invention. Further, the average particle diameter D of the glass powder₅₀Preferably about 2 to 20 μm. If necessary, a sealing material was prepared by adding various refractory filler powders to the glass powder.

Next, a carrier is added to the glass powder (or the sealing material) and kneaded, thereby preparing a glass paste (or a sealing material paste). The vehicle 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 viscosity increasing agent, or the like can be added as necessary.

The organic solvent is preferably an organic solvent having a low boiling point (for example, a boiling point of 300 ℃ or less), containing little residue after firing, and not causing glass to change in quality, 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, and the like are preferably used. In addition, as the organic solvent, higher alcohols are more preferably used. The higher alcohol itself has viscosity, and therefore can be made into a paste without adding a resin to the carrier. Furthermore, pentanediol and a derivative thereof, specifically, diethylpentanediol (C)₉H₂₀O₂) Also, since the adhesive is excellent in viscosity, it can be used in a solvent.

The resin is preferably contained in an amount of 0.1 to 20% by mass, because the resin has a low decomposition temperature, causes little residue after firing, and hardly causes glass deterioration. 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 the sealed portion between the first member including metal, ceramic, or glass and the second member including metal, ceramic, or glass using a coater such as a dispenser or a screen printer, dried, and heat-treated at 300 to 500 ℃. By this heat treatment, the glass powder is softened and fluidized, and the first and second members are sealed.

The glass composition and the sealing material of the present invention can be used for coating, filling, and the like, in addition to sealing applications. The paste may be used in a form other than paste, specifically, in the form of powder, circuit board, tablet, or the like.

Examples

The present invention is explained in detail based on examples. Tables 1 and 2 show examples of the present invention (sample Nos. 1 to 11) and comparative examples (sample Nos. 12 and 13).

[ Table 1]

[ Table 2]

First, glass raw materials such as various oxides and carbonates were mixed with the glass components shown in the table to prepare a glass batch, and then the glass blank was put into a platinum crucible and melted at 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 (rod-in-mold thermal expansion coefficient measurement), and the other molten glass was formed into a film shape by a water-cooled roll. Samples for TMA were obtained by subjecting nos. 2, 8, 9 and 11, which did not contain the refractory filler, 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, the glass powder obtained and the refractory filler powder were mixed with the samples nos. 1,3 to 7, 10 and 12 in which the refractory filler was mixed, to obtain mixed powder.

Refractory filler powder using Zr₂WO₄(PO₄)₂(in the table, noteZWP), NbZr (PO)₄)₃(in the table, it is represented as NZP). The refractory filler powder has an average particle diameter D₅₀About 10 μm.

The obtained mixed powder was calcined at 430 ℃ for 10 minutes to obtain a sintered body. The obtained sintered body was used as a specimen for TMA.

The samples No.1 to 12 were evaluated for glass transition point, thermal expansion coefficient, softening point and fluidity.

A sample for TMA was measured by using a TMA apparatus for measuring the glass transition point and the thermal expansion coefficient (30 to 150 ℃).

The softening point was measured by a macro-type differential thermal analyzer. The measurement was carried out in the 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 put into a mold having a diameter of 20mm, press-molded, and then sintered at 430 ℃ for 10 minutes on a glass substrate. The flow diameter of the sintered body was 19mm or more, which was indicated by ". smallcircle", and the flow diameter of the sintered body was less than 19mm, which was indicated by ". times".

As is clear from the tables, samples Nos. 1 to 11 of examples of the present invention are excellent in fluidity. On the other hand, the sample No.12 of the comparative example excessively contained K₂O and thus devitrified upon sintering. Sample No.13 excessively contained K₂O, and MoO₃Is 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.