JPS62171942A - Sintered glass powder - Google Patents

Abstract

PURPOSE:To obtain sintered glass powder having high density and low dielectric constant and useful as a multi-layer printed circuit board, low-resistance metallic material, etc., by crushing a glass having a specific composition, forming the powder and sintering the formed glass powder. CONSTITUTION:Glass raw materials are compounded to form a principal composition consisting of 40(wt)%<=SiO2<=60%, 10%<=Al2O3<=30% and 20%<=MgO<=40% and 10-30% of the MgO is made to be substituted with one or more kinds of metal oxides selected from SrO, CaO and BaO. The obtained raw material mixture is melted in a crucible at about 1,500 deg.C. The molten mixture is thrown into water to obtain frit, which is crushed to powder having an average particle diameter of 1-10mum. The powder is kneaded in the presence of toluene, etc., formed to a sheet, etc., heated at 875-1,000 deg.C spending about 5hr and sintered by keeping the above state for about 3hr.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a glass powder sintered body obtained by firing a molded body of powder obtained by pulverizing glass.

[Background technology]

In recent years, ceramics have been widely used in the field of electronic materials.

As the demand for miniaturization and high reliability increases for multilayer wiring boards that are equipped with highly integrated LSIs and a large number of various elements,
The use of multilayer wiring boards made of ceramic materials is expanding. Ceramic multilayer wiring boards are usually made of alumina (A
A green sheet is formed using 1zOs as the main material, and conductor wiring made of a high melting point metal (Mo, W, etc.) is printed on the green sheet by thick film technology. Thereafter, a multilayer green sheet obtained by laminating these green sheets together is fired at a high temperature of about 1500 to 1600° C. in a non-oxidizing atmosphere. However, in the multilayer wiring board mainly made of alumina as mentioned above, the transmission time of the signal propagating through the board wiring becomes longer due to the high dielectric constant of alumina and the ultra-fine refractory metal wiring with high resistance value. , it was difficult to meet the demand for faster speeds.

To solve this problem, low resistance metal materials (Au, Ag, Ag-Pd5C) are used instead of high resistance and high melting point metal materials.
Although it is conceivable to form interconnections using materials such as
If the main material is alumina, the temperature is much lower than the firing temperature of the substrate, so it cannot be used in practice. In other words, a material is required that can perform sufficient sintering at a substrate firing temperature of about 1000° C. or lower.

To meet this requirement, glass materials are used.
Especially S i Ox A l z O s M g O
A glass powder sintered body obtained by firing a glass powder mainly composed of is often used.

However, S i Ch A 12 O3Mg
The temperature for melting the raw materials for O-based glass is 1500°C.
In order to exceed the
There is a problem that the crucible is severely damaged. SiO□, A
N to l2O3 and MgO to lower the melting temperature.
Although there are compositions with additions of alkali metals such as a and lithium, the problem is that if Na or Li enters the sintered body, a migration phenomenon occurs and the insulation, which is one of the important characteristics of a substrate, deteriorates. There is.

In addition, many materials contain ZnO, TiO□, etc. in their composition, but if even a trace amount of Zn○ or TiO□ is included, it is difficult to form a dense sintered body and the specific inductivity tends to increase, which is not preferable. .

[Purpose of the invention]

In view of the above circumstances, this invention has been developed to achieve sufficient densification by firing at a low temperature of 1000°C or less, and to have a low dielectric constant (
Furthermore, even when used as a multilayer wiring board material, there is no concern about insulation deterioration due to migration phenomena, and it is also suitable for forming wiring using low-resistance metal materials, and has a low melting temperature of 5tOx Al103 MgO-based glass powder sintered body. The purpose is to provide

[Disclosure of the invention]

In order to achieve the above object, the present invention provides a glass powder sintered body obtained by firing a molded body of powder obtained by pulverizing glass, wherein the composition expressed in weight percent of the glass is 40≦S i
The basic composition is Ot≦60 10≦Al2O3≦30 20≦MgO≦40, of which 10 for MgO
~30% by weight SrO, CaO, and B a''O
The gist of the present invention is a glass powder sintered body characterized by being substituted with at least one metal oxide selected from the group consisting of:

Hereinafter, the glass powder sintered body (hereinafter simply referred to as "sintered body") according to the present invention will be explained in detail.

The reason why the composition of the glass used to create the glass powder is limited as described above is as follows.

When the composition ratio of S i O* exceeds 60% by weight, the melting temperature increases and it becomes difficult to obtain a dense sintered body.
When it is less than 0% by weight, the firing temperature and the crystal pore temperature rise, so that sufficient crystallization cannot be achieved at a firing temperature of around 1000°C, and it becomes difficult to form a dense sintered body.

When the composition ratio of AlzOs exceeds 30% by weight, 100%
Sufficient sintering cannot be achieved at a firing temperature of 0° C. or lower. 1
When it is less than 0% by weight, it tends to form a SiO□-MgO-based crystal phase, resulting in a high dielectric constant and poor practicality.

When the composition ratio of MgO exceeds 40% by weight, the temperature
Sufficient sintering cannot be achieved at temperatures below. 10% by weight
If the temperature is less than 1, crystallization will be too intense and it will be difficult to form a dense sintered body.

When the amount of SrO, BaO and CaO substituted exceeds 30% by weight, either the degree of sintering or the meltability deteriorates. When it is less than 10% by weight, the melting properties become significantly worse, the degree of sintering and the relative dielectric constant deteriorate, and the practicality becomes poor.

Next, the present invention will be described in detail based on specific examples and comparative examples.

Each metal oxide is blended in the proportions shown in Examples 1 to 21 in Table 1 and Comparative Examples 1 to 4 in Table 2.

SiC2, A 1. The three powders of t Os and MgO are calcined at 1000 to 1200° C. to remove moisture prior to blending. The blended glass raw material powders are thoroughly mixed, placed in a crucible, and melted at a heating temperature of 1500°C. The molten liquid thus obtained is dropped into water to obtain a glass frit. The obtained frit is pulverized into powder with a suitable particle size (average particle size of about 1 to 10 nm).

Next, for example, polybutyl methacrylate resin, dibutyl phthalate, toluene, etc. are added to the glass powder and kneaded, followed by defoaming treatment under reduced pressure to form a slurry. after that,
Using this slurry, a continuous dry sheet with a thickness of 0.2 fl was formed on a film sheet by a doctor blade method. This dry sheet was peeled off from the film sheet to create a green sheet of an appropriate size. Then, a plurality of these green sheets were stacked and formed into a molded body using a mold press, and then fired. In firing, the temperature was raised to 875 to 1000°C over 5 hours, this state was maintained for 3 hours, and then allowed to cool to obtain a sintered body.

The relative permittivity and water absorption of the sintered bodies of Examples and Comparative Examples were measured, and the results are shown in Tables 1 and 2.

The meltability of the glass is also shown in the table. Meltability was determined from the ease of flow of the melt in the crucible when the blended glass raw material powder was held at 1500° C. for 3 hours and then taken out. The symbols in the table are used with the following meanings.

◎ Most of the melt in the crucible can be poured out, and almost no melt remains in the crucible (meltability: very good).

○ A considerable amount of the melt in the crucible can be poured out, and about 1/3 to 1/4 of the total amount of melt remains in the crucible (meltability:
good).

△ Approximately half of the total amount of melt in the crucible can be flowed out (normal meltability).

× Although the melt inside the crucible flows slightly, it cannot flow out of the crucible (meltability: poor).

×× The melt in the crucible does not even flow. Alternatively, no vitrification occurred at all (meltability: completely poor). The water absorption rate for determining sinterability was measured in accordance with JIS C-2141. In addition, the measurement frequency of the relative permittivity is IMI (
It is z.

As shown in Table 1, the sintered bodies of Examples 1 and 2 satisfy meltability, sinterability, and dielectric constant at the same time.

Moreover, this was achieved at a firing temperature of 950''C, which is less than 1000℃.As shown in Table 2, the sintered body of the comparative example does not simultaneously satisfy the three properties listed in -h. Can not.

〔Effect of the invention〕

The sintered body according to the present invention is not only dense with cordierite as the main crystal phase and has a low dielectric constant, but also can be achieved at a firing temperature of 1000°C or less. , the composition does not contain alkali metal additives that cause migration phenomena. Therefore, since it is dense and has a low dielectric constant, the sintered body is suitable for multilayer wiring board materials, and
Since the firing temperature is 0° C. or lower, a low-resistance metal material can be printed and fired at the same time to form wiring, thereby increasing the signal propagation speed. Furthermore, since there is no concern about migration phenomena, high insulation properties can be maintained, and since the composition has a low glass melting temperature, it is easy to manufacture, so it is possible to reduce costs at the manufacturing stage.

Claims (2)

[Claims] (1) In a glass powder sintered body obtained by firing a molded body of powder obtained by crushing glass, the weight percent composition of the glass is basically 40≦SiO_2≦60 10≦Al_2O_3≦30 20≦MgO≦40 Regarding the composition, 10 of them are MgO.
A glass powder sintered body characterized in that ~30% by weight is substituted with at least one metal oxide selected from the group consisting of SrO, CaO, and BaO. (2) The glass powder sintered body according to claim 1, wherein the powder obtained by crushing glass has an average particle size of 1 to 10 μm.