JPS60198703A - Resistor composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a resistor composition suitable as a material for a resistor paste for a thick film resistor, and more particularly, to a resistor composition suitable as a material for a resistor paste for a thick film resistor.

It is applied as a paste to an unfired porcelain sheet and is non-oxidized.
11: This invention relates to a resistor composition capable of producing a thick film resistor by firing in an atmosphere.

Conventional technology (mW @ 6 sheets) (raw sheet) is coated with nickel paste or copper paste and opened in a predetermined pattern.

A multilayer ceramic circuit board can be obtained by stacking several layers, heat-pressing them at °C, and firing them in a non-oxidizing atmosphere. By using such a multilayer ceramic circuit board, it is possible to miniaturize a single circuit device. However, when constructing a circuit device using this multilayer ceramic circuit board.

It was necessary to attach many chip-like elements to the multilayer ceramic circuit board, and it was difficult to achieve significant miniaturization. If a resistor composition that can be fired in a non-oxidizing atmosphere emerges, it would be possible to apply resistor paste together with conductor paste to a green sheet and fire it, making it possible to significantly downsize a single-circuit device. become. However, at present, the above-mentioned resistor compositions and pastes that are put into practical use have not yet appeared.

OBJECTS OF THE INVENTION A second object of the present invention is to provide a resistor composition that can be fired in a non-oxidizing atmosphere.

Structure of the Invention The present invention to achieve the above object is as follows:] LO to 70.
0 parts by weight of molybdenum silicide and 1.0 to 71.0 parts by weight of calcium fluoride and strontium fluoride.

and a small amount of barium fluoride (both 1 m of metal fluoride and
The present invention relates to a resistor composition comprising 10.0 to 80.0 parts by weight of glass.

Effects of the Invention A resistor paste is made using the resistor rod assembly based on the above invention, printed on a raw porcelain sheet, and baked at a temperature of 1050°C to 1250°C in a non-oxidizing atmosphere. For example, a thick film resistor having practically usable characteristics can be obtained. Therefore, a base metal thick film resistor can be formed simultaneously with the formation of a thick film conductor using a base metal conductor paste such as nickel. As a result, it is possible to contribute to miniaturization and cost reduction of circuit devices.

Example 1 Next, a resistor composition according to an example of the present invention and a method for forming a multilayer ceramic circuit board using the same will be described.

First, silicon dioxide (5ift) 7s, o parts by weight, zinc oxide (ZnO) 5.5 parts by weight, zirconium oxide (Z
r0x) 12-ONks, carbonic acid 2 #shiro, 1.
3.071 LtK parts of (CaCO2) and -55 weight of aluminum oxide (Al*Om) were mixed and melted in an aluminum crucible at 1400'C for 30 minutes, and the bath melt was poured into water and rapidly cooled. .

This glass is crushed to about 50 μm in an alumina mortar,
Further, this was placed in a polyethylene-backed bot mill together with ethanol, and ground with alumina balls for 150 hours to obtain powdered glass with a particle size of 10/7 m or less.

Next, the above glass, 1Mot3j, and CaFt were weighed in the proportions shown in Table 1, and mixed in a ball mill at ℃. Then, this mixture 91JZ 12 in argon gas atmosphere
Heat treatment was performed at 00°C for 1 hour. and.

This was placed in a polyethylene-lined bot mill with nY ethanol and ground for 24 hours with an alumina ball.

An alloy powder with a diameter of 105 m or less, preferably 5 μm or less was obtained. The composition of this alloy powder (resistance string v) is substantially the same as the composition of the initial raw material.

Thereafter, 100 parts by weight of this alloy powder and 25 parts by weight of trocellulose dissolved in 90 parts by weight of phthyl carbitol in an organic binder were mixed into 3 parts by weight.
This was kneaded using this roll mill to obtain a resistor paste of about 800 poise.

On the other hand, a raw porcelain sheet for Y printing (based on the above resistor) was produced by the following method. A1.0m powder 50m, li
i, Sin, powder bed 20-@Okibe, SrO powder 25i
Ceramic raw material powder consisting of part ii, IN amount of Li2O powder, and 4 parts by weight of MgO powder, binder consisting of a water bath solution of acrylic acid ester polymer, glycerin, carboxylic acid salt, and water were each placed in a ball mill. Add, mix, and make a slip.

After defoaming treatment, the thickness is 200mm using the doctor grade method.
It's been a long time since I've been producing micrometer-long raw sheets. and.

From this raw sheet, 9mm x 9mm and 6mm x
A 9 mm piece of the two-glue raw sheet was cut out.

Next, as shown in Fig. 1, nickel (a conductive base made by kneading NiJ powder and an organic binder at a ratio of 3:1) was printed on the former layer of the chemically modified sheet using a K200 mesh screen. By drying at 125° C. for 10 minutes, an Nl conductor film (2) was formed as shown in FIG.

Next, by screen printing P1 with the resistor paste and conductive paste according to the present invention and drying,
A resistor film (3) was formed as shown in FIG.

Next, the other raw sheet piece (41) of the size indicated by the chain line was stacked on top of the pile of raw sheet pieces, and heated at 100°C.

Thermocompression bonding was carried out at 150 kg/cm2, and this was heat-treated at 500°C in an oxidizing atmosphere to blow off the organic binder.

(98.5% by volume) + H2 (1-5% by volume) in a reducing atmosphere at 1200°C for 2 hours, as shown in Figure 2, in porcelain AI (la) (4a). A multilayer ceramic circuit board for a hybrid integrated circuit having a thick film conductor (2a) and a thick film resistor (3a) was completed.
The size of the part of a] that does not overlap the conductor (2a) is 3r
nmX 3 mm (Yes, and the film thickness is 18 pm.

Next, when we measured the sheet resistance of this resistor (3a) at 25°C using the bridge method and added 1 to the resistance temperature coefficient in the temperature range of 25°C to 125°C, the results in Table 1 were obtained. Obtained.

As is clear from the above, a thick film resistor can be obtained by applying the resistor paste of the single-layer embodiment onto a raw porcelain sheet and firing it in a reducing atmosphere. Therefore, the base metal paste such as Ni can be fired at the same time. Therefore, it is possible to provide a thick film resistor in the ceramic layer together with a thick film conductor based on Ni or the like, and the cost and size of the hybrid integrated circuit can be reduced.

Also, as is clear from Table 1 (.

Glass 10.0-80.0 parts by weight.

Mo, Sl　19.0~70.0ilEft　Sound b.

CaF* ] -0~71-ON placement part, 1111 composition, sheet resistance 7.95 ~ 12,
A thick film resistance of 150°000Ω/hole can be obtained.

Therefore, by appropriately selecting the six composition ratios, any resistance value can be obtained.

Also, the temperature coefficient of resistance is -1998 to +953 pI)m
/” Since the C trap is contained, it is possible to provide a practical resistance.

Example 2 In order to confirm that the same effects as in Example 1 can be obtained even if the composition of the glass is changed, glass powder was prepared as follows. 75.0 parts by weight of silicon dioxide (S'02),
Diboron trioxide CB, Os) 13. Oi! E Dobe 10.0 parts by weight of calcium oxide (CaCOx) and 2.9 parts by weight of aluminum oxide (A1.0.) were mixed.

Powdered glass was obtained in the same manner as in Example 1.

Next, this glass and MoBSi and CaF,y(
The powder of the resistor composition was obtained by mixing the powder shown in Table 2 in the same manner as in Example 1, and using this powder, a multilayer ceramic circuit board with the same structure was formed in the same manner as in Example 1. Then, the electrical characteristics were measured in the same manner as in Example 1.

As is clear from Example 2, there is no significant difference in resistance characteristics even if the glass composition is changed.

In other words, the glass used in the present invention is not necessarily limited to a single composition. In addition.

Example] Sin, -ZnO-ZrO, -Ca
O-AI.

03 series glass, 5in2-Boo, -ca of Example 2
o -AI20J glass has a working point (]
The glass has a temperature of 900 to 1,200°C at which it has a 10' whistle.

The glass of the resistor composition of the present invention is not limited to the glasses having the compositions of Examples 1 and 2, but has a working point of 900 to 1200°C and is resistant to metallization when fired in a reducing atmosphere. - metal oxides (Pbo, 5noffi.

It has been confirmed that any composition may be used as long as it does not contain Bi, O, etc.).

Example 3 In order to ensure that the same effect as in Example 1 can be obtained even if the metal fluoride is changed, 5 rpm of metal fluoride was prepared, and a glass with a four-composition as in Example 1 and Mo3Si were prepared. and S
rF* was weighed in the proportions shown in Table 3, and the heat treatment temperature in an argon inert atmosphere was set at 900°C.
A resistor composition was formed in the same manner as in Example 1. Thereafter, a resistor paste was prepared using the same method as in Example 1, and a multilayer ceramic circuit board was also prepared, and the electrical percentage was measured.

The results shown in Table 3 were obtained.

As is clear from Table 3, even when < -5rFt k is used, substantially the same effects as in the case of CaF can be obtained.

Example 4 MoSi as molybdenum silicide, τBa as metal fluoride
In order to confirm that the same effects as in Example 1 can be obtained even when Fx is used, glass having the same composition as in Example 1,
MoSi, , BaF, were weighed in the proportions shown in Table 4, and a resistor composition powder was prepared in the same manner as in Example 1.
Please use this in the same manner as Example 1.

Make resistor paste Y and then make a multilayer porcelain board.

When its electrical characteristics were measured, the results shown in Table 4 were obtained.

Example 5 Glass having the composition of Example 1, M o 81 m and SrF,
A resistor composition powder was prepared in the same manner as in Example 1 except that the powder was weighed in the proportions shown in Table 5 and the heat treatment temperature in argon inert gas was 900°C. A resistor paste was made using the same method as in Example 1, a multilayer ceramic circuit board was made, and the electrical percentage was measured, and the results shown in Table 5 were obtained. As is clear from this table (,
Molybdenum silicide.

Even if the properties of the metal fluoride are changed, the same effects as in Example 1 can be obtained.

Example 6 In order to confirm that the same effect as in Example 1 can be obtained even when molybdenum silicide iMo, Si, binding, and fluoride metal sheets are used, glass having the same composition as in Example 1,
Mo5Si3.5rF1, BaF, 'l Weighed in the proportions shown in Table 6, heat treated in argon gas at temperature y
A powder of a resistor composition was made in the same manner as in Example 1 except that the temperature was 100° C., and a paste was made using this powder in the same manner as in Example 1, and a multilayer ceramic circuit board was made.
Measuring the electrical characteristics.

The results shown in Table 6 were obtained. As is clear from this result,
Even if multiple types of metal fluoride are used, the same effects as in the case of 1 m can be obtained as long as the amount is within the range of 1 to 71 parts by weight.

Variations The invention is not limited to the embodiments described above.

For example, the following modifications are possible.

(al) When using three types of fluorinated gold paste, molybdenum silicide can be used as Mo, Si, Mo5t, Mo,
It has been confirmed that the same effect as in Example 1 can be obtained even when a combination of multiple types of Si, etc. is used.

(bl) It has been confirmed that it is desirable to keep the firing temperature of the mixture of glass, molybdenum silicide, and metal fluoride in the range of 900 to 1200°C. It may be carried out in an atmosphere, in a vacuum, in a neutral atmosphere, or in a reducing atmosphere.

(The organic binder for making CI resistor paste is
Resins such as ethyl cellulose, turpentine oil.

It may also be one that has been bathed in a high boiling point solvent such as butyl carpitol acetate. Also, the amount of this binder is 15 to 35
It is preferable to use about parts by weight.

The atmosphere when firing the resistor together with the Idl main sheet may be a neutral atmosphere.

(e) It is desirable that the raw sheet, resistor, and ring body be fired in a non-oxidizing atmosphere at a temperature in the range of 1050 to 1250°C.Before this firing.

It is desirable to perform a second heat treatment in an oxidizing atmosphere at 400 to 600°C to decompose the organic matter.

+f1 The resistor composition of the present invention can of course be used in a state other than a paste.

[Brief explanation of the drawing]

FIG. 1 shows a multi-NI! according to an embodiment of the present invention. FIG. 2 is a plan view showing the ceramic circuit pattern, and FIG. 2 is a cross-sectional view showing the multilayer ceramic circuit board after firing at the portion that curves along line 1--0 in FIG. 11+... raw sheet piece, (21... conductor film, (3j
...Resistor membrane. (4)...Raw sheet piece. Agent Noriji Takano

Claims (1)

[Claims] il+ 19.0-70. ONOkibe's molybdenum silicide. 1.0-71. At least one kind of paulownia fluoride selected from calcium fluoride, strontium fluoride, and barium fluoride of ON51 part. 10.0-80. Om: A resistor composition consisting of Okibe glass. (2) The molybdenum silicide is 3 molybdenum silicide, 2 molybdenum silicide,
1. A resistor composition containing at least one of molybdenum silicide and tri-molybdenum silicide. (For 31iiJ glass, one working point is 900 to 1200℃.
The resistor Mi composition according to claim 1 or 2, which falls within the range of .