JPS63215549A - Electric resistor and manufacture - 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 Field of Industrial Application The present invention relates to a thick film type electrical resistor provided on a fixed chip resistor or a circuit wiring board, etc., and particularly to a thick film type electrical resistor that can be obtained by firing in a non-oxidizing atmosphere. Possible electrical resistors and.

It relates to its manufacturing method.

Conventional technology The electrical circuits of electronic devices are often constructed by mounting various electrical elements such as resistors, capacitors, diodes, and transistors on circuit boards, but as electronic devices become smaller, these Circuit boards that can further increase the packaging density of electrical elements have come into widespread use.

The resistors installed on these circuit boards are either thick film resistors formed by printing and baking resistor material paste directly onto the circuit, or a pair of electrodes formed at both ends of a square plate-shaped ceramic chip. There are also fixed chip resistors in which the thick film resistor is formed so as to span both electrodes.

Conventionally, in order to provide such a thick film resistor on a circuit board,
For example, a conductive material paste such as Ag or Ag-Pd is applied to the surface of an alumina substrate obtained by firing at around 1500°C, and after baking, a paste containing RuO□ as a resistor material is applied by screen printing, etc. It is common practice to apply the film, then bake it at 750 to 850° (4'), and then adjust the resistance value by trimming or the like if necessary.

However, in recent years, electronic devices have become lighter, thinner, and smaller.
The demand for lower costs has become even stronger, and efforts are being made to further reduce the size and cost of circuit boards.

As concrete measures to reduce the size of the former, firstly, the circuit board is multilayered, and secondly, the resistor is built inside. Examples of multilayer circuit boards include Ag uN &
:! A multilayer wiring board obtained by laminating and crimping ceramic green sheets (raw sheets) printed with a conductive material paste such as Ag-Pd type, and then simultaneously firing in the atmosphere at 800 to 1)00 °C, and An example of internally incorporating a resistor is obtained by further applying RuO□-based resistance material antibody material paste on a ceramic green sheet printed with the conductor material paste, laminating and crimping in the same manner as above, and then co-firing. Multilayer wiring boards with built-in resistors are known.

In addition, as a specific measure to reduce the cost of the latter, in place of expensive noble metal conductor materials such as Ag or Ag-Pd materials, inexpensive base metal conductor materials such as Ni or Cu can be used. Green ceramics are heated at 800 to 1) 00°C in a neutral or reducing non-oxidizing atmosphere such as nitrogen gas or hydrogen-containing nitrogen gas that can avoid high resistance due to oxidation. Multi-layered layout obtained by simultaneous firing! Ill? One board has been put into practical use. Furthermore, as described in Japanese Patent Application Laid-Open No. 56-153702, a resistor material made of Mo5iz-TaSi2 and glass is coated on an alumina substrate having an m (C1) conductor, and the thickness obtained by heat treatment is Film resistors and the like are also known.

Problems to be Solved by the Invention However, in order to reduce the size and cost of circuit boards at the same time, Ru0z-based resistor materials have problems when co-fired with green ceramics in a nitrogen gas or hydrogen-containing nitrogen gas atmosphere. A reduction reaction occurs, and the resistance value decreases, so that it no longer exhibits characteristics as a resistor.

Furthermore, when a resistor material made of MoSi, -TaSiz, and glass is co-fired with a green ceramic sheet in a non-oxidizing atmosphere, the fired body may warp due to differences in the expansion and contraction rates of the two, and the MoSi□ -Ta
There is a problem that gas is generated due to the decomposition reaction of Siz, which tends to cause blistering in the fired product. In order to improve this, as described in JP-A-50-198703, there is a known example in which a resistor material made of MoS i z-metal fluoride (e.g. calcium fluoride) and glass is used. There is no warping or blistering during firing as mentioned above.

However, the thick film resistor obtained by applying this MoS i z -metal fluoride and glass resistor material to a green ceramic sheet and co-firing it exhibits a An increase in resistance value of ~10% was observed, and the desired function as a resistor could not be performed.

Further, the above-mentioned conventional electric resistor has a temperature change coefficient of resistance value not smaller than 1000 ppm/''C, which is problematic as a resistor element for a circuit that requires precise operation.

Therefore, in another application filed on the same day as this application, we proposed that not only can it be used as a fixed chip resistor, but it can also be mounted on a circuit board using a base metal conductor, laminated, fired, and incorporated into a multilayer board to maintain a stable resistance value. It was shown that it is possible to obtain an electrical resistor.

However, it has been desired to further reduce the temperature change coefficient of the resistance value of this electrical resistor.

An object of the present invention is to provide an electrical resistor that can not only be used in fixed chip resistors or general circuit boards, but also can be laminated with base metal conductor materials and incorporated into multilayer boards, and which The object of the present invention is to provide an electrical resistor that can reduce the coefficient of change.

Another object of the present invention is to provide a manufacturing method that can improve the characteristics of the electrical resistor.

Means for Solving the Problems In order to solve the above problems, the present invention is characterized by having a fired body containing a molybdate of zirconium and/or hafnium and a fluoride of an alkaline earth metal. The object of the present invention is to provide an electrical resistor.

Further, the present invention heat-treats a resistor material containing as a main component at least one of zirconium and/or hafnium molybdate and its precursor, and an alkaline earth metal fluoride, and An electric resistor comprising firing a resistor material obtained by heat treatment to obtain a fired body containing a zirconium and/or hafnium molybdate and an alkaline earth metal fluoride. A method for manufacturing a resistor is provided.

Next, the present invention will be explained in detail.

The molybdate of zirconium and/or hafnium in the present invention includes, for example, ZrMozO) 1fMOz
Examples include a single substance such as Os or a mixture thereof. Molybdates consisting of multiple of these metals can also be used, for example (Zr, Hf, ) Mow's, where x + y = 1
These are exemplified, and these can be used alone or in combination with the above-mentioned individual substances or mixed substances.

Such zirconium and/or hafnium molybdates can be synthesized by heat treatment of oxides of the respective metals and molybdenum oxide (Mob), but they can also be synthesized by heat treatment using their precursors. You can also do it.

In the present invention, it is preferable to use a binder,
Examples of this include glass, and the glass used is generally known glass, and is not limited to glasses with a specific composition, such as Pbff0a, Big
Oxides such as h3, Snug, and CdO may be reduced and metallized when the resistor material containing them is fired in a non-oxidizing atmosphere, and this metal changes the resistance value. If such occurrence is undesirable, it is preferable not to contain these oxides.

The glass component is 5iOz1B! o3, ZnO, C
aO1SrO5Zr02 etc. are preferable, and the composition ratio of these oxides is: Si0□12-33 wt% Btus 20-35 wt% ZnO or 5r013-33 wt% CaO10-2
5% by weight Zr0z 15-45% by weight is preferred.

In order to manufacture glass from a composition of these oxides, the respective oxides are weighed and mixed to achieve the above composition ratio. This mixture is placed in a crucible and melted at a temperature of 1200 to 1500°C, and then the molten liquid is poured into water, for example.
Rapidly cool to obtain coarse glass powder.

Glass powder is obtained by pulverizing this coarse powder to a desired particle size (for example, 10 μm or less) using a pulverizing means such as a ball mill or a vibration mill.

In the above, a mixture of pure oxides was used, but the glass is not limited to this, as long as the result is a mixture of each oxide. It may be melted to make glass. For example, CaO (calcium oxide) is CaC0z (calcium carbonate), BJz (
Since boron oxide) can be obtained by heat treatment of boric acid (HzBOs), CaC0* and II□B03 can be used in place of part or all of CaO and Bz(h, respectively. Regarding oxides of other components The same is true.

Further, the alkaline earth metal fluoride used in the present invention is represented by the general formula MeFz when Me is a metal, and Me is an alkaline earth metal, that is, Mg, C
It is preferable to use one kind or a mixture of two or more of these metal salts.

However, not only these alkaline earth metal fluorides but also other metal fluorides can be used.

The zirconium and/or hafnium molybdates, glass powder, and alkaline earth metal fluorides obtained as described above may be mixed and used as a resistor material as is, but they may be heat-treated and pulverized. It is preferable to use this material as a resistor material in view of the resistance temperature characteristics of a resistor obtained by firing it. The heat treatment temperature is 80
A temperature of 0°C to 1200°C is preferable; if the temperature is outside this range, the resistance value of the finished resistor will not be affected by slight fluctuations in the composition ratio due to work conditions in each step of processing the resistor material into an electrical resistor. It is difficult to stably obtain a desired resistance value. This heat treatment is preferably performed in a non-oxidizing atmosphere, and it is preferable to use not only nitrogen gas and other active gases, but also a mixed gas containing hydrogen gas.

The composition ratio of each component of the resistor material is 40 to 95% by weight of zirconium and/or hafnium molybdate, 4.5 to 59.5% by weight of glass powder, and 0.5 to 30% by weight of alkaline earth metal fluoride. Weight percent is preferred. If the content of zirconium and/or hafnium molybdate is too low and the content of glass is too high, the resistance value of the fired electrical resistor may become too high, which is undesirable. Alternatively, if the amount of hafnium molybdate is too large and the amount of glass is too small, the sinterability during firing may deteriorate and it may not be possible to stably hold it on a circuit board. However, when the resistor is embedded in a laminated circuit board, the amount of zirconium and/or hafnium molybdate and alkaline earth metal fluoride may be greater than the above range, and may be 100%.

Furthermore, even if the alkaline earth metal fluoride is less than 0.5% by weight or more than 30% by weight, the temperature change coefficient of the finished electrical resistor will be greater than ±500 ppm/'c, which is preferable. There may be no. However, materials outside this range can also be used as long as the temperature change coefficient of resistance is improved.

To create a resistor for a fixed chip resistor or a thick film resistor from the resistor material powder obtained in this way, for example, the resistor material powder is applied to a ceramic green sheet and fired. In order to carry out this coating, a vehicle is mixed with these resistor material powders to prepare a coating liquid so that, for example, silk screen printing can be performed. This vehicle is preferably one that can be burned out in the pre-firing stage, and for this purpose, the resin is dissolved or dispersed in an organic vehicle, that is, an organic solvent, and if necessary, a plasticizer,
It is preferable to add various additives such as a dispersant. Examples of the organic solvent include butyl carbitol acetate, butyl carbitol, and turpentine oil, and examples of the resin include cellulose derivatives such as ethyl cellulose and nitrocellulose, and other resins.

The usage ratio of this organic vehicle and the resistor material powder varies depending on the organic solvent, resin, etc. used, but the usage ratio of the organic solvent and resin is 20 to 50% by weight for the former and 80% for the latter.
~50% by weight is suitable. These components are made into a paste using a mixing means such as a three-roll mill or a sieve.

The resistor material paste obtained in this way is applied to a substrate and further processed as described below to create a resistor.This substrate is coated with a ceramic green sheet that is fired together with conductor material and resistor material. In addition to the method in which a ceramic green sheet is fired in advance, a resistor material and a conductor material are further applied thereto, and then fired.

These can also be applied when forming a laminate.

The ceramic green sheet includes, for example, aluminum oxide (Alt(h) 35-45% by weight, silicon oxide (Sin2) 25-35% by weight, boron oxide (B, 0% by weight),
ff) 10-15% by weight, calcium oxide (Cab)
7-13% by weight, magnesium oxide (MgO) 7-1
For example, a slurry prepared by mixing 0% by weight of an oxide mixture of ceramic constituents with an organic vehicle using a ball mill or the like may be formed into a sheet using a doctor blade or the like. At this time, when glass is not used in combination with zirconium and/or hafnium molybdate, the ceramic green sheet may contain a large amount of glass to produce the same effect as when glass is used in combination.

The organic vehicle is comprised of an acrylic resin such as an acrylic ester, a resin such as polyvinyl butyral, a plasticizer such as glycerin or diethyl phthalate, a dispersant such as a carboxylic acid salt, and a solvent such as water or an organic solvent.

The resistor material paste is applied to a ceramic green sheet by means such as silk screen printing,
After drying, it is preferable that the resin component is decomposed and burned by heat treatment at 400 to 500°C.

At this time, a paste of a base metal conductor material such as Ni or Cu or a noble metal conductor material such as Ag or Ag-Pd is also applied to the ceramic green sheet in the same way as the resistor material paste coating film, and the paste is also applied to the ceramic green sheet in the same way as the resistor material paste coating. will be processed.

This base metal conductor material such as Ni or Cu or Ag
Alternatively, a paste composition of Ag-Pd noble metal conductor material is exemplified by adding 2 to 15 weight % of glass flift to 98 to 85 weight % of each metal powder.

In this way, the resistor material and/or conductor material is incorporated into the ceramic green sheet, but in the case of a fixed chip resistor, only the surface of this unfired substrate is incorporated, and in the case of a thick film resistor of a multilayer substrate, the resistor material and/or the conductor material are incorporated into the ceramic green sheet. The body material and conductor material assembled in an unfired state are further laminated to form a predetermined circuit, and then fired. By this firing, the conductor material and/or the thick film resistor material can be made into a fired body at the same time as the substrate.

In this case, when a base metal conductor material such as Ni or Cu is used as the conductor material, it is preferable to sinter it in a non-oxidizing atmosphere in order to prevent the resistance value from increasing due to oxidation, and the sintering temperature is as follows: For example, 800℃ to 1) 00℃
, 0.5 hours to 2 hours. As the non-oxidizing atmosphere, nitrogen gas, other active gases, and mixed gases containing these gases and hydrogen gas may also be used. Also, Ag or A
When g-Pd noble metal conductor material is used, it can also be fired in an oxidizing atmosphere such as air.

A circuit wiring board incorporating a conductor and/or a resistor is completed as described above, but cracks, distortions, and distortions may occur not only between the fired board and the conductor but also between the fired board and the resistor due to firing. In addition to not causing blistering, the resistance value of the resistor is suppressed to change within ±2% even if it is left in a high humidity atmosphere for more than 1000 hours, ensuring high reliability. The temperature change coefficient of the value can also be set to, for example, ±500 ppI1)/'c or less. This is due to the resistor's good matching with the conductor and fired substrate, and the unique moisture resistance of the resistor, which is made of a fired body of zirconium and/or hafnium molybdate, alkali metal fluoride, and glass. It is thought that this is the case, but the details are not clear.

In addition, zirconium and/or hafnium molybdate and alkaline earth metal fluoride can be recognized in the resistor by xvA diffraction analysis.

In the present invention, a molybdate of zirconium and/or hafnium may be used as described above, but instead of the molybdate of zirconium and/or hafnium, a molybdate of zirconium and/or hafnium may be used by heat treatment. It is also possible to use some or all of the precursors.

In any of these cases, it is preferable to mix it with glass and heat treat it, then crush it and use it as a resistor material. It is also possible to directly create a resistor by applying it to a ceramic sheet, then heating it to remove organic matter, and then firing it.

In addition, the glass may be placed in a state where the mixed material of oxides constituting it is fired together with zirconium and/or hafnium molybdate and alkaline earth metal fluoride, and these oxides A precursor of zirconium and/or hafnium molybdate and/or its precursor, a part or all of this oxide together with an alkaline earth metal fluoride are made into a paste state as described above, and this is applied to a substrate. In the process of combustion of organic matter and subsequent firing, a glass consisting of the above glass components is formed, which is combined with molybdate of zirconium and/or hafnium and/or its precursor, and fluoride of alkaline earth metal. Any material may be used as long as it can be fired to produce a resistor. For example, CaO, which is a component of glass materials,
(Calcium oxide) is heating CaCO5 (calcium carbonate), B20ff (boron oxide) is boric acid (H2BO3)
Therefore, CaC0= and HJ(h can be used instead of part or all of CaO and BzO*, respectively.

The resistor material used in the present invention may be one whose main components are zirconium and/or hafnium molybdate, glass, and alkaline earth metal fluoride as a result of the treatment process.

Example Next, the present invention will be explained in detail.

Example 1 Each component was weighed and mixed to have the composition shown in Table 1 in terms of oxide.

Table 1 In the table, the unit is weight%.

The respective mixtures of Glass 8 and Glass B were individually melted at 1400° C. in an alumina crucible, and the melts were poured into water and rapidly cooled. Take out this quenched material, put it in a pot mill with ethanol, and use an alumina pole for 24 hours.
The glass powder was pulverized for a period of time to obtain a glass powder with a particle size of 10 μm or less.

Additionally, zirconium molybdate was obtained from molybdenum oxide and zirconium oxide.

Next, the glass powders of Glass A and Glass B obtained above, the zirconium molybdate and the alkaline earth metal fluoride obtained above were weighed and mixed in the proportions shown in Table 2. .

Table 2 (When using zirconium molypide 1 and fluoride together) (XMI) Table 2 (7'j) 1000℃ in gas atmosphere
The powder was heat-treated for 1 hour, and then ground with ethanol in a bot mill and dried to obtain a resistor material powder of glass, molybdate, and fluoride heat-treated powder having a size of 10 μm or less.

Next, 25 parts by weight of an organic vehicle (90 parts by weight of butyl carbitol, 10 parts by weight of ethyl cellulose) were added to 100 parts by weight of the resistor material powder of each sample and mixed in a roll mill to obtain a resistor material paste.

On the other hand, A'ltO+ 40.0% by weight, SiO□3
5.0% by weight, Ih0s13.0% by weight, Ca07.0
% by weight, 100 parts by weight of a ceramic raw material powder consisting of 5.0 parts by weight of MgO, 8 parts by weight of polyvinyl butyral, 8 parts by weight of diethyl phthalate, 0.5 parts by weight of oleic acid, 10 parts by weight of acetone, 20 parts by weight of isopropyl alcohol, and 20 parts by weight of methyl ethyl ketone was added and mixed in a ball mill to prepare a slurry, and after defoaming treatment, a long ceramic green sheet with a thickness of 200 μm was prepared using a doctor blade method. A green sheet piece with a length of 9 fins and a width of 9n+ and a green sheet piece with a length of 6 s and a width of 9 fins were cut out from this ceramic green sheet.

Next, as shown in FIG.
Butylcarpitol 2 is added to the weight part as an organic vehicle.
A conductor material paste prepared by adding 0 parts by weight and 5 parts by weight of ethyl cellulose and mixing them using a three-roll mill was silk screen printed and dried at 125° C. for 10 minutes to form a thick conductor material coating film 2. Next, the resistor material paste obtained above was silk screen printed on the green sheet piece 1 in the same manner as described above, and dried at 125° C. for 10 minutes to form a resistor material coating film 3.

Next, on green sheet piece 1, the length 6 mm and width 9 obtained above are
Stack the green sheet pieces 4 on top as shown by the chain lines in the diagram,
This is then heat-bonded at 100°C and 150kg/cj at 400-500°C in an oxidizing atmosphere such as air to form green sheet piece 1.4, conductor material coating 2, and resistor material coating 3. Decompose and burn each residual organic matter.

After removing organic matter in this way, N, 9B, 5v
o1%, Hz 1.5 vo1% mixed gas, 95
After firing at 0°C for 1 hour, as shown in FIG. Thick film conductor 2a, thick film resistor 3a of fired body of resistor material coating 3
We have completed a multilayer ceramic substrate with In this multilayer substrate, no warpage or bulges as shown in FIGS. 3 and 4, which will be described later, were observed.

The multilayer ceramic substrate of the fired body (sample N01) thus obtained was polished in the layer direction to expose the resistor layer,
This exposed resistor layer was analyzed by X-ray diffraction (alpha rays for Cu), and the obtained results are shown in Figure 5, which confirms the type of molybdate and fluoride in the specimen. I was able to do that.

Next, the resistance value (Rzs) of this multilayer ceramic substrate 3a at 25°C and the resistance value (Rzs) when heated to 125°C are calculated.
, □, ) were measured using a digital multimeter, and the temperature coefficient of resistance (TCP) was determined using the following equation.

Shown in 2.

In addition, the multilayer ceramic substrate obtained above was heated at 60°C for 9
25℃ after 1000 hours under 5% relative humidity
Table 2 shows the results of measuring the resistance value and calculating the rate of change.

In addition, each electrical resistor made using a sample from which the alkaline earth metal fluoride was removed was measured in the same manner as above, and the obtained results were compared to the sample magnets in Table 2. are shown in Table 3.

Example 2 A multilayer ceramic substrate was fabricated from the resistor materials shown in Table 4 in the same manner as in Example 1, except that hafnium molybdate was used instead of zirconium molybdate. R□, TCP, and resistance change rate were determined and shown in Table 4.

Note that a multilayer ceramic substrate was fabricated using a resistor material excluding the alkaline earth metal fluoride in the same manner as above, and the measured values and calculated values were measured in the same manner as above for sample N.
o, are shown in Table 5 in correspondence.

Example 3 In Example 1, part of the zirconium in the zirconium mo177'7'7 salt was replaced with hafnium. Table 6
A multilayer ceramic substrate was fabricated from the resistor materials shown in Table 6 in the same manner except that the molybdate shown in Table 6 was used, and R□, TCR, and rate of change in resistance were determined in the same manner as in Example 1. Shown below.

In addition, in Example 3, a multilayer ceramic substrate was produced in the same manner as in Example 1, except that the resistor material corresponding to each sample in Table 6, which does not contain alkaline earth metal fluoride, was used.
Similarly, R2S, TCR, and resistance change rate were determined and shown in Table 7 in correspondence with the sample number.

Example 4 In Example 1, zirconium and hafnium molybdates were used instead of zirconium molybdates.
A multilayer ceramic substrate was fabricated from the resistor materials shown in Table 8 in the same manner except that a mixture of at least one species was used, and R2, TCP, and resistance change rate were determined in the same manner as in Example 1 and these are shown in Table 8. .

In addition, in Example 4, a multilayer ceramic substrate was produced in the same manner as in Example 1, except that the resistor material corresponding to each sample in Table 8, which does not contain alkaline earth metal fluoride, was used.
Similarly, Ls, TCP, and resistance change rate were determined, and these are shown in Table 9 in correspondence with the sample number.

Example 5 In Example 1, nitrogen (Nz) for the mixture of molybdate, alkaline earth metal fluoride and glass powder
A multilayer ceramic substrate was prepared from the resistor materials shown in Table 13 in the same manner as above, except that no heat treatment was performed at 1000°C for 1 hour in a gas atmosphere of 98.5vo1%, hydrogen (Hz) 1.5vo1%. As in Example 1, Rzs,
TCP, the resistance value change rate was determined and shown in Table 10.

Although not shown, the type of molybdate and the type of fluoride can be confirmed by X-ray diffraction analysis of the fired bodies of each of the examples.

Table 3 (When zirconium molybdate and fluoride are not used together) 14 (When hafnium molybdate and fluoride are used together) αm Table 4 (Second) Table 5 (When hafnium molybdate and fluoride are used together) (When fluoride is not used in combination) Table 6 (When zirconium or hafnium molybdate and fluoride are used together) 0 Carp 13R7 (
Table 8 (Mixture of molybdates of zirconium and hafnium and fluoride (when used in combination with agar) C; t81M%+
) Table 9 (2 old fluorocarbons (without arsenic material) Table 10 (molybdate and fluorocarbons) (no heat treatment of arsenic material and glass) (XJM'■Comparative example 1 (MoSiz-Ta
Sfz glass resistor material) MoSiz 16 parts by weight,
A mixture of 9 parts by weight of Tacit was heated in air at 1400° C., and the product was ground with ethanol in an alumina pole in a Bottle mill for 24 hours and dried to obtain a fine powder of 10 μm or less. BaO, Btus, MgO, CaO, StO□
and an organic vehicle (20 parts of butyl calpitol, 5 parts of ethyl cellulose).
25 parts by weight) were added and mixed in a roll mill to obtain a resistor material paste.

A multilayer ceramic substrate was obtained in the same manner as in Example 1 except that this resistor material paste was used.

As a result, we formed a resistor material coating on a ceramic green sheet, heat-treated it, removed the material, and fired it simultaneously, and found that both fired bodies had different expansion and contraction rates. As a result, warping can be seen as shown in Figure 3.
Furthermore, 5iOz gas was generated by the decomposition reaction of Mo5iz and TaSi, causing blistering as shown in FIG. 4, making it impossible to put it to practical use. Note that lla is the ceramic layer 1a, 14a is the ceramic layer 4a, and 13a is the ceramic layer and thick film resistor corresponding to the thick film resistor 3a, respectively.

Comparative example 2 (MoSi, -BaF, glass-based resistor material)
70 parts by weight of MoSiz, 20 parts by weight of BaFz, and 5
Mixing with 10 parts by weight of glass lift consisting of iOz, Zn, Zr0z, Ca0z, Alt03 in a ball mill,
The obtained powder was heated at 1200 °C in an argon (Ar) gas atmosphere.
After heat treatment at ℃, it was ground with ethanol in an alumina ball in a bot mill for 24 hours, dried and
A fine powder of µm or less was obtained.

A multilayer ceramic substrate was obtained in the same manner as in Example 1 except that this resistor material paste was used.

Table 1) shows the Rzs, TCP, and rate of change in resistance value obtained for the thick film resistor of this multilayer ceramic substrate in the same manner as in Example 1.

From the above results, the multilayer ceramic substrates of the examples have no warping or blistering, and the rate of change in resistance value is within ±2%, and the TCR is ±500 ppm/' especially in the case where the resistor material is heat treated. c, whereas the multilayer ceramic substrate of Comparative Example 1 shows warping, and the multilayer ceramic substrate of Comparative Example 2 has a rate of change in the resistance value of the resistor that is four times larger.

Effects of the Invention According to the present invention, it is possible to supply an electrical resistor containing a molybdate of zirconium and/or hafnium and a fluoride of an alkaline earth metal. If a resistor material having a composition containing metal fluoride as a main component is used, for example, to form a resistor by simultaneously firing a ceramic green sheet together with a base metal conductor material in a non-oxidizing atmosphere, the firing The body does not warp or bulge, and not only can the temperature change of the resistor be reduced, but the temperature change coefficient of the resistance value of the resistor can be reduced to, for example, ±500 ppm/''C or less. .

As a result, it is possible to meet the demands for both miniaturization and cost reduction of circuit boards incorporating resistors, and it is also possible to provide excellent electronic components for electronic devices that require precise operation.

Additionally, by heat treating zirconium and/or hafnium molybdates and alkaline earth metal fluorides, the absolute value of the temperature change coefficient of the resistor can be reduced compared to those that are not treated, and precision operation is not required. It can add excellent performance to electrical circuits.

[Brief explanation of the drawing]

Fig. 1 is a diagram showing an example of a state in which a resistor material coating film and an electrode material coating film before firing are formed on a substrate to form a multilayer structure when manufacturing the electrical resistor of the present invention, and Fig. 2 is a cross-sectional view of the fired body, FIG. 3 is a cross-sectional view of the fired body formed into a multilayer structure using conventional resistor material, and FIG. 4 is an explanatory diagram when gas is generated in the fired body. FIG. 5 is an X-ray diffraction diagram of an electrical resistor according to an embodiment of the present invention. In the figure, 1.4 is a green sheet piece, 2 is a conductive material coating,
3 is a resistor material coating, 1a and 4a are ceramic layers, 2a is a thick film conductor, and 3a is a thick film resistor. February 28, 1988 Figure 1 Figure 3 Figure 4

Claims (5)

[Claims] (1) An electrical resistor characterized by having a fired body containing a molybdate of zirconium and/or hafnium and a fluoride of an alkaline earth metal. (2) The fired body contains at least one of zirconium and/or hafnium molybdate and its precursor;
Claim 1, characterized in that the resistor material is fired from a resistor material containing an alkaline earth metal fluoride as a main component.
Electrical resistor described in section. (3) The main component of the resistor material is 40 to 95% by weight of at least one of zirconium and/or hafnium molybdate and its precursor in terms of the zirconium and/or hafnium molybdate; Alkaline earth metal fluoride 0.5-30% by weight and glass 4.5%
3. The electrical resistor according to claim 2, wherein the electrical resistor comprises 59.5% by weight. (4) At least one of zirconium and/or hafnium molybdate and its precursor as a main component;
A resistor material containing an alkaline earth metal fluoride as a main component is heat-treated, and the resistor material obtained by this heat treatment is fired to produce a molybdate of zirconium and/or hafnium and an alkaline earth metal. A method for producing an electrical resistor, the method comprising obtaining an electrical resistor made of a fired body containing a fluoride. (5) The main component of the resistor material before heat treatment is zirconium and/or hafnium molybdate and at least one of its precursors, which weighs 40 to 95% in terms of the zirconium and/or hafnium molybdate. %, 0.5 to 30% by weight of alkaline earth metal fluoride, and 4.5 to 59.5% by weight of glass. Production method.