JPS59207853A - Glass composition - Google Patents

Abstract

PURPOSE:To prepare electrically insulating glass of circuit of thick film, by providing a glass composition consisting of glass powder having a specific composition and a filler, specifying the glass powder and the filler. CONSTITUTION:A glass composition consisting of 70-99wt% glass powder, and 1-30wt% filler. The glass powder consists of 41-50wt% SiO2, 2-15wt% Al2O3, 30-45wt% BaO, 5-20wt% ZnO, 0.5-2wt% CaO+MgO, 0.5-4wt% ZrO2, 0.1-1.5wt% SnO2 and 0.05-1.5wt% K2O. The filler is shown by the formula ZrSiO4, 2MgO.SiO2, Al2O3. When an electrically insulating layer of circuit of thick film is made of this composition, PbO or B2O3 will not be diffused into a conductive material during the calcination process of the upper conductive material formed on it, so the conductive material has extremely high wetting properties to solder.

Description

[Detailed description of the invention] The present invention relates to glass compositions.

A single-layer thick film circuit component in which a resistor and a conductor circuit are formed on an insulating substrate by a thick film method, an insulating layer is formed on the circuit, and an upper conductor is formed on the insulating layer, and multiple circuits are formed through the insulating layer. Multilayer thick film circuit components have been proposed as electronic components. The glass for the disconnection layer of such parts is PbO-B2O3-6.
i02 series glass is known.

However, such glass has the disadvantage that during the firing process of the upper conductor, PbO or B2O3 diffuses into the conductor and floats onto the conductor, resulting in a significant deterioration of solder wettability when attaching terminals, etc. to the upper conductor. there were. In addition, the resistance change rate and variation of the resistor due to firing were large, and the target resistance value was obtained.

It is an object of the present invention to provide a glass composition that solves the above f, ) + H points and has a uniform force.

That is, the present invention consists of a glass powder of 70 to 99% by weight and a filler of 1 to 30% by weight, and the glass powder has a weight ratio of SiO24] to 50 A12032 to]5BaO3.
0~45 Zn0. 5-20 CaO+MgO0.5~2 ZrO20.5~4 SnO20.1~1.5 R200.05~15 (R is Li, Na and/or K), and the filler is ZrSiO4° 2Mg0-8i0
2 and/or Al2O3.

When the insulating layer of a thick film circuit is formed using the composition according to the present invention, P-o
Since O or B2O3 does not diffuse into the conductor, the solder wettability with the conductor is extremely good. Furthermore, since the insulating layer has very little influence on the resistor in the circuit when fired, the rate of change and variation in the resistance value of the resistor is extremely small.

The composition according to the present invention is effective as a glass for an insulating layer of a thick film circuit, but it can also be used as a binder glass for forming conductors or resistors by a thick film method by adding conductive powder to the composition. can.

The composition according to the present invention is prepared by kneading a suitable vehicle to form a paste, and applying the paste by screen printing or the like.
A glass layer is formed by forming a glass layer. Part of the crystallization occurs during this firing process, and the crystals mainly consist of BaA12.
Although it is Si○8, a trace amount of 3BaO-8iC1s is also included.

The reasons for limiting the composition according to the present invention are as follows.

The filler in the composition is added for the purpose of reducing the reaction between the glass and the conductor or resistor during the firing process. Specifically, ZrSiO4, ZrO2゜2Mg0.5iOz, or Al2O3 are desirable because they can achieve this purpose and are relatively easy to obtain.

In the composition of the present invention, 1 to 30% by weight of filler is added as the balance of the glass powder, but if it is less than Jφ, the above purpose will not be achieved, and if it is more than 30J, the glass component will be insufficient and the dense glass will not be formed. A layer is difficult to form. The filler is preferably in the range of 2 to 25]i in the above range.

The glass powder 5102 is a glass network former, and is also a component of crystals that partially precipitate during firing. If S io 2 < 41 weight crack, the softening temperature will be too low and the circuit pattern will be easily deformed due to excessive fluidity during firing, and the reactivity with conductors and resistors will increase and there is a risk of damaging their characteristics. I don't like it because it is. On the other hand, S
If iO2>50'lj, the solubility during production of glass powder decreases, the softening temperature increases, and the firing temperature becomes too high, which is not preferable. S]02 is more preferably in the range of 41 to 48% by weight within the above range.

Al2O3 is a component of the precipitated crystals. Al2O3<2
If the concentration is too low, crystals will precipitate and become thin, and if Al2O3>15% by weight, it will become vitrified and become short. Among the above ranges, Al2O3 is preferably in the range of 3 to 14 times -Jt't%.

BaO functions to improve the solubility when producing glass powder, and is also a component of precipitated crystals. BaO<3
If it is 0% by weight, the softening temperature of the glass will become too high and the firing temperature will become too high, which is not preferable. Also, Bad
If it is >45% by weight, the coefficient of thermal expansion becomes too large, making it difficult to apply it to substrates such as alumina. Ba
Among the above ranges, O is preferably in the range of 31 to 42%.

ZnO has the effect of improving solubility in glass powder production. When Zno<5% by weight, the softening temperature of the glass is too high. If ZnO>200% by weight, the softening temperature of the glass is too low, the circuit pattern may be deformed during firing, the conductor,
There is a risk that the reactivity with the resistor will increase and the characteristics will be impaired. ZnO
is more preferably in the range of 8 to 18% by weight within the above range.

CaO and MgO have the function of preventing devitrification that occurs during the melting process during glass powder production and the function of adjusting the rate of crystal formation that precipitates during firing.

When CaO+MgO<0.5% by weight, this effect is small, and when CaO+MgO>2fi- the coefficient of thermal expansion of the glass becomes too large, both of which are unfavorable. Oa
O+MgO is 1-1.5 i'i! in the above e range! A range of % is more desirable.

Z r O2 has the effect of increasing the softening point of the glass after firing and the effect of adjusting the precipitation rate of crystals during firing.

When ZrO2<0.5% by weight, such effects are insufficient, and when Z;roz>4:i, the softening temperature of the glass becomes too high, both of which are unfavorable. ZrO2 is more preferably in a range of 1 to 3 ft% within the above range.

5 nOz is added to improve the water resistance and acid resistance of the glass. When 5nOz<0.1% by weight, the above effect due to addition is small, and even if more than 1.5% by weight is added, the effect does not improve. 5nC1z is 05 to 1 in the above range
A weight range is more desirable.

R20 (R is Li, Na and/or K) has the effect of lowering the softening temperature of glass and improving chemical durability, especially acid resistance. R20〈005 heavy ftz
%, this effect is insufficient, and when R20 > 1.5% by weight, the coefficient of thermal expansion becomes too large (too much, both of which are unfavorable.) desirable.

The composition according to the invention can be manufactured as follows.

Each raw material is weighed, mixed and melted to achieve the target composition using a conventional method. Next, the molten glass is formed into a plate or flake shape, and glass powder is produced by water crushing or mechanical crushing. Next, the composition of the present invention is manufactured by mixing the glass powder and filler in a predetermined ratio.

The composition prepared in this way is kneaded with a suitable organic vehicle and used after being made into a paste.

Ag, C! It can be made into a conductive paste by adding conductive metal particles such as u.
Further, by adding resistive particles such as RuO2, a resistor paste can be obtained. These pastes can be used to form insulating layers, conductors, and resistors by printing in a conventional manner and then firing at a temperature of 850 to 950°C.

Example After weighing and mixing each raw material to obtain a glass with the target composition shown in Table 1, this was placed in a crucible, and 140011500
It was heated to °C and dissolved with stirring for 2-3 hours. A fused glass powder was then produced. Next, this glass powder and filler were weighed so as to have the proportions shown in the same table, and mixed while being finely pulverized in a bot mill to produce the compositions shown in the same table. Note that the particle size of the glass powder and filler powder is preferably 45 μm at maximum and 2 μm or less on average when forming a fine pattern.

In order to investigate the properties of glass made from this composition, the above composition was mixed with 95% α-terpineol and 5% ethyl cellulose.
It was made into a paste by adding an organic vehicle consisting of This paste was printed and fired to form a glass layer, and the properties described in the same table were measured for this glass layer, and the results are also listed. Note that the data sheet 7 in the table is a conventional one and is shown for comparison.

As is clear from the table, the composition according to the present invention is excellent in that the rate of change in resistance value of the resistor is extremely small.

The characteristic values shown in the same table are as follows.

This is the resistance value Ω at room temperature when DC 100V is applied to the insulation resistance glass.

Dielectric constant: R direct at room temperature when a voltage of K) 12 is applied.

3 in a Pb-5n eutectic solder bath containing Dip for a second and pull out. This results in 90% or more of the conductor surface area is solder Those that were wet were considered good.

Scanning basket microscope cross section of sintered glass Observe if there are no bubbles. And so.

Measure the resistance value of the penis. then Apply glass paste to this resistor. The resistance value of the resistor is Measure. The insulation layer is formed before This shows the change in resistance value of the resistor afterward.

(+ is due to forming an insulating layer. This indicates that the resistance value has increased. )

Claims (3)

[Claims] (1) Glass powder 70~99% and filler 1~
It consists of 30 views, and the glass powder is 5i02 41 ~ 50A1203 in the regular m area display.
2 ~ ]5Ba, 0
30 ~45Zn0
5 ~20CaO+Mg0 0.5
~2zrO205~ 4 SnO20,1~1.5 to 20 0.05~15 (R is L
i, Na and/or K), and the filler has a composition in the range of Zr5iO<. 2Mgo-8102 and/or A12C)3. (2) The glass powder has a weight rating of 5102
4'1~48A1203
3~14BaO31~42 Zn0 8~18CaO+Mg0
1~15 ZrOz 1~3SnO20,5
i+it5 according to claim 1, which has a composition in the range of ~ I R2o O1~ 1
Composition of. (3) Claim 1, comprising the glass powder 75-98% by weight and the filler 2-25%.
The sealing composition according to item 32.