JP2000072475A - Powdery glass, its production and glass-ceramic composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make the oxygen content of an oxide glass in a powdery glass higher than that of a stoichiometric compsn. by filling a ball mill with an atmosphere contg. a specified amt. of oxygen and grinding glass bodies in the mill. SOLUTION: Melted and molded glass bodies are put in a ball mill, this ball mill is filled with an atmosphere contg. >=30 vol.% oxygen and the glass bodies are ground to obtain the objective powdery glass. The objective glass- ceramic composite material consists preferably of 30-70 wt.% of the powdery glass and 70-30% ceramic powder. The powdery glass preferably releases >=1,000 μl gaseous oxygen per 1 m2 surface area in the temp. range from 100 deg.C to the pour point. The powdery glass is not limited if it is mixed with an org. binder and used. One or more selected from alumina powder, mullite powder, zirconia powder, forsterite powder and cristobalite powder are appropriately used as the ceramic powder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powdered glass, a method for producing the same, and a glass-ceramic composite material using the powdered glass.

[0002]

2. Description of the Related Art In general, powdered glass is produced by melting a glass raw material, forming it into a film through a water-cooled roller, and then pulverizing it in a ball mill. Adhesive material,
Widely used as sealing material, coating material and filling material.

In recent years, a substrate material using powdered glass has also been developed. When manufacturing this substrate material, first, powdered glass and ceramic powder are mixed at a predetermined ratio, and then an organic binder is further mixed. Then, a method of forming into a sheet is adopted.

Normally, a multi-layer circuit is formed by printing a conductive paste on the sheet material in a predetermined pattern, and then firing at a temperature of about 800 to 1000 ° C. in a state where a plurality of the conductive pastes are laminated. A multilayer glass ceramic substrate is made.

[0005] However, when a multilayer glass ceramic substrate is manufactured, the number of laminated sheet materials is large,
When firing in a nitrogen atmosphere, the removal of the organic binder in the sheet was insufficient, and carbon remained inside, resulting in problems such as a decrease in bending strength and insulation resistance of the substrate and a grayish color of the substrate. .

As a means for solving such a problem, Japanese Patent Application Laid-Open No. Hei 6-338664 discloses a method in which an oxidizing agent such as antimony oxide, arsenic oxide, cerium oxide, or vanadium oxide is added to powdered glass, so It has been proposed to improve the scattering property of the organic binder in the sheet material and sufficiently remove the organic binder.

[0007]

SUMMARY OF THE INVENTION
When an oxidizing agent is contained as a composition of the powdered glass as in -338664, the valence of the obtained glass changes depending on the temperature and the melting atmosphere when the glass raw material is melted. As a result, when the powdered glass is fired, Fluctuates in the amount of oxygen released,
This is not practical because the scattering effect of the organic binder becomes unstable.

The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide a method for manufacturing a multilayer glass ceramic substrate without adding an oxidizing agent as a composition of powdered glass to a sheet. It is an object of the present invention to provide a powdered glass capable of completely removing the organic binder and a method for producing the same, and a second object of the present invention is to provide a glass-ceramic composite material using the powdered glass.

[0009]

SUMMARY OF THE INVENTION The powdered glass of the present invention comprises:
The oxide glass is characterized in that the oxygen content is present in excess of the stoichiometric oxygen content.

The method for producing a powdered glass of the present invention is a method for producing a powdered glass in which a melt-molded glass body is put into a ball mill and pulverized.
The glass body is pulverized in an atmosphere containing oxygen as described above.

Further, the glass-ceramic composite material of the present invention is characterized in that the oxide glass comprises a powdered glass in which the oxygen content is in excess of the stoichiometric oxygen content, and a ceramic powder.

[0012]

In the powdered glass of the present invention, the oxygen content of the oxide glass exists in excess of the oxygen content of the stoichiometric composition.
The amount of oxygen released from the powdered glass during firing is increased.

That is, in the case of a powdered glass having an oxygen content of a normal stoichiometric composition, a temperature from 100 ° C. to a pour point (° C.)
In a temperature range of about 600 μm per 1 m ^{2 of} surface area
1 or less, but in the case of the powdered glass of the present invention, it is possible to release 1000 μl or more of oxygen gas.

As a result, even when the powdered glass of the present invention is mixed with an organic binder and formed into a sheet, the number of laminated sheets is increased, and even when the glass is fired in a nitrogen atmosphere, the organic binder is easily scattered. It is possible to remove the organic binder. Incidentally, the pour point means a temperature at which the glass is heated and softened and flown.

In order to produce the powdered glass of the present invention, the melt-molded glass body is placed in a ball mill, and then the inside of the ball mill is crushed in an atmosphere containing at least 30% by volume of oxygen.

Further, the glass-ceramic composite material of the present invention preferably comprises 30 to 70% by weight of powdered glass and 70 to 30% by weight of ceramic powder.

That is, if the amount of the powdered glass is more than 70% by weight, the bending strength of the substrate is greatly reduced, and conversely, the weight is 30% by weight.
If the amount is less, the substrate will not be dense, pores will be generated, and the desired insulating property will not be obtained.

As the powdered glass used in the present invention, any one can be used as long as it is generally used by mixing with an organic binder. For example, SiO ₂ —B ₂ O ₃ —R ₂ O-based glass, PbO ₂ -B ₂ O ₃ -Al ₂ O ₃ based glass, SiO ₂
-ZnO-B ₂ O ₃ based glass is suitable.

The ceramic powder may be selected from alumina powder, zirconia powder, mullite powder, forsterite powder, and cristobalite powder according to the required characteristics (bending strength, insulation, thermal expansion coefficient, dielectric constant, etc.) of the finished product.
Or two or more persons may be used as appropriate.

[0020]

The present invention will be described below in detail based on examples and comparative examples.

Example 1 First, SiO ₂ 6 was used in weight%.
_{0%, B 2 O 3 30} %, Na 2 O 5%, K 2 O5% of the glass raw material was prepared so as to have the composition, which was placed in a platinum crucible, after being melted for one hour at 1600 ° C., this The glass melt was formed into a film through a water-cooled roller.
Next, this film-shaped glass body is put into a ball mill,
After sealing the ball mill, the inside was evacuated and the glass was pulverized for 8 hours while injecting oxygen. The ball mill used was a cylindrical shape having a diameter of 20 cm and a height of 20 cm, in which a plurality of alumina balls were put, and the inside of the ball mill was an atmosphere containing 40% by volume or more of oxygen.

With respect to the thus obtained powdered glass having an average particle diameter of 3 μm, the amount of oxygen released from 100 ° C. to the pour point (750 ° C.) was measured using a quadrupole mass spectrometer manufactured by Balzers. 1264μ per 1m ^{2 of} surface area
1 of oxygen gas.

Next, 50% by weight of this powder glass and 50% by weight of alumina powder having an average particle size of 2 μm were mixed.
Based on 100 parts by weight of this mixture, 12 parts by weight of an acrylic resin as an organic binder and 3% by weight as a plasticizer
Of butyl benzyl phthalate and 50% by weight of toluene as a solvent to form a slurry, formed into a sheet having a thickness of 200 μm by a known doctor blade method, and dried at 80 ° C. for about 2 hours.

Next, the sheet material is cut into a predetermined size, and via holes for connecting upper and lower conductors are formed. Then, a conductive paste is embedded in these via holes and a wiring pattern is printed. went. Here, as the conductor, a conductor paste containing Ag as a main component was used and printed at a predetermined position by a screen printing method. Eight green sheets thus obtained are laminated and thermocompressed, and then heated at a rate of 20 ° C./min to 900 ° C.
The multi-layer glass ceramic substrate was manufactured by performing the calcinations in the air.

The thus obtained multilayer glass ceramic substrate was cut into a size of 15 × 50 mm, placed on two fulcrums of 30 mm, and a load was applied to the center between the fulcrums at a speed of 0.5 mm / min to break the substrate. When the bending strength was measured by a three-point load test method for measuring the load at the time of
kgf / cm ² .

Further, the volume resistivity of the multilayer glass ceramic substrate was measured at 150 ° C. based on JIS C2141.
Was 10 ¹⁴ Ω · cm.

When the appearance of this substrate was visually observed, the color tone was white.

Example 2 First, PbO 85
%, B ₂ O ₃ 11%, SiO ₂ 2%, Al ₂ O ₃ 2%, and prepare a glass raw material at 900 ° C.
For 1 hour and then formed into a film through a water-cooled roller. The thus obtained film-shaped glass molded body was pulverized in the same manner as in Example 1 to produce powdered glass suitable for sealing a semiconductor package.

With respect to the powdered glass thus obtained, 1
When the amount of released oxygen from 00 ° C. to the pour point (400 ° C.) was measured, 1173 μl of oxygen gas was released per 1 m ^{2 of} surface area.

Next, 60% by weight of this powdered glass, 20% by weight of a lead titanate powder having an average particle size of 8 μm, and an average particle size of 10%
After mixing 20 μ% of zirconium silicate powder of μm,
10 parts by weight of an acrylic resin was mixed as an organic binder with 100 parts by weight of this mixture, followed by granulation.

Further, a molded body of 10 × 10 × 50 mm was prepared from the granules by a metal mold press as a sample for measuring bending strength, and 50 × 10 × 50 mm as a sample for measuring volume resistivity.
A molded body of 50 × 10 mm was produced. Next, these molded bodies were fired at 420 ° C. at a heating rate of 10 ° C./min in air to obtain measurement samples.

When the bending strength of this measurement sample was measured, it was as high as 810 kgf / cm ^2, and the package could be sealed well. The volume resistivity was measured to be as high as 10 ^13.5, and it was possible to prevent a signal short circuit between the leads, and it had good characteristics as glass for sealing a semiconductor package.

(Comparative Example 1) Powdered glass was produced under the same conditions as in Example 1 except that the film-shaped molded product was pulverized in the air, and the amount of oxygen released from 100 ° C to the pour point of the powdered glass was measured. Was 577 μl per 1 m ^{2 of} surface area.

Next, using this powdered glass, a multilayer glass-ceramic substrate was produced under the same conditions as in Example 1.
The flexural strength was measured to be 1500 kgf / cm ² , and the volume resistivity was measured to be 10 ⁹ Ω · c
m, which were lower than those of Example 1.
The color tone of this substrate was colored gray.

(Comparative Example 2) Powdered glass was produced under the same conditions as in Example 2 except that the film-shaped molded product was pulverized in the atmosphere, and the amount of oxygen released from 100 ° C to the pour point of the powdered glass was measured. Was 421 μm per 1 m ^{2 of} surface area.

Next, using this powdered glass, a multilayer glass-ceramic substrate was produced under the same conditions as in Example 1.
When its bending strength was measured, it was 680 kgf / cm ²
And the volume resistivity was measured and found to be 10 ^11.5 , which was also lower than that of Example 1. The color tone of this substrate was colored gray.

In the above embodiment, an example was described in which the powdered glass of the present invention was used for a multilayer glass ceramic substrate and a sealing glass for a semiconductor package. However, the powdered glass of the present invention is not limited to this. Instead, for example, it can be used in various applications including a dielectric layer formed on a plasma display panel substrate used by mixing powdered glass and an organic binder to form a paste.

[0038]

As described above, the powdered glass of the present invention can sufficiently remove the organic binder in the sheet without containing an oxidizing agent in the powdered glass.
Particularly, it is suitable as a glass-ceramic composite material in which ceramic powder and an organic binder are mixed and fired.

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Claims (6)

[Claims] 1. A powder glass characterized in that the oxygen content of the oxide glass is present in excess of the stoichiometric oxygen content. 2. The powdered glass according to claim 1, wherein at least 1000 μl of oxygen gas is released per 1 m ^{2 of} surface area in a temperature range from 100 ° C. to a pour point (° C.). 3. A method for producing a powdered glass in which a melt-molded glass body is put into a ball mill and ground, wherein the glass body is ground in an atmosphere containing at least 30% by volume of oxygen in the ball mill. Manufacturing method. 4. A powder glass wherein the oxygen content of the oxide glass is present in excess of the stoichiometric oxygen content;
A glass-ceramic composite material comprising a ceramic powder. 5. A glass-ceramic composite material according to claim 3, comprising 30 to 70% by weight of powdered glass and 70 to 30% by weight of ceramic powder. 6. The glass-ceramic composite material according to claim 4, wherein the ceramic powder is at least one of alumina powder, mullite powder, zirconia powder, forsterite powder, and cristobalite powder.