JPS63215551A - 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. This invention relates to a possible electrical resistor and 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 coated on 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. A common method is to apply the film, then bake it at 750 to 850°C, 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 or A.
Examples include multilayer wiring boards obtained by laminating and crimping ceramic green sheets (green sheets) printed with conductor material paste such as g-Pd, and then simultaneously firing them in the atmosphere at 800 to 1100°C; As an example of internalization, a RuO□ resistance material antibody material paste is further applied on a ceramic green sheet printed with the conductor material paste, laminated and crimped in the same manner as above, and then co-fired to create a resistor body. Multilayer wiring boards and the like 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. These are co-fired with green ceramics at 800-1100℃ in a neutral or reducing non-oxidizing atmosphere such as nitrogen gas or nitrogen gas containing hydrogen, which can avoid high resistance due to oxidation. Multilayer wiring boards obtained by this method have been put into practical use. Furthermore, as described in Japanese Patent Application Laid-Open No. 153702/1982, a resistor material made of Mo5iz-TaSiz and glass is coated on an alumina substrate having a copper (Cu) 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, Ru01-based resistor materials cannot be used simultaneously with green ceramics in nitrogen gas or nitrogen gas atmospheres containing hydrogen. When fired, a reduction reaction occurs, resulting in a low resistance value and no longer exhibiting properties as a resistor.

Furthermore, when a resistor material made of MO5iz-TaSig and glass is co-fired with a green ceramic sheet in a non-oxidizing atmosphere, the fired body may warp due to the difference in expansion and contraction rates between the two, and the MoSig-TaSig
There is a problem that gas is generated due to the decomposition reaction of Sit, which tends to cause blisters in the fired product. In order to improve this, it is known that a resistor material made of Mo5iz-metal fluoride (e.g. calcium fluoride) and glass is used, as described in JP-A-60-198703. , No warping or blistering during firing as mentioned above was observed.

However, when the thick film resistor obtained by coating this Mo5iz-metal fluoride and glass resistor material on a green ceramic sheet and co-firing it, the resistance of 5 to 10 % increase in resistance value is observed, and the prescribed function as a resistor cannot 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 the present application, fixed chip resistors can not only be used, but also be provided on a circuit board using base metal conductors, laminated, baked, 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 The present invention solves the above problems by using niobium and/or
Alternatively, the present invention provides an electrical resistor characterized by having a fired body containing tantalum molybdate and an alkaline earth metal fluoride.

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

Next, the present invention will be explained in detail.

In the present invention, molybdates of niobium and/or tantalum include, for example, NbJozO+4, TaJozOt4
Examples include single substances such as these or mixtures thereof. Molybdates consisting of a plurality of these metals can also be used, for example (Nbz Tay )MOsO+a, where x +y
=2, etc., and these can be used alone or in combination with a plurality of substances, or in combination with each of the above-mentioned individual substances or mixed substances.

Such niobium and/or tantalum sibdates are composed of oxides of the respective metals and molybdenum oxide (MOO
Although it can be synthesized by heat treatment in 3), it can also be synthesized by heat treatment using its precursor.

In the present invention, it is preferable to use a binder,
Examples of this include glass, and the glass used is one that is well known, and is not limited to glasses with specific compositions, such as Pb3O4, Bi2O2
% 5nOz, CdO can be reduced and metallized when resistor materials containing them are fired in a non-oxidizing atmosphere, and this metal changes the resistance value. It is preferable not to contain these oxides in cases where it is undesirable for such occurrence to occur.

Glass components include Sing, th03, ZnO, C
aO1SrO5zrO2 etc. are preferable, and the composition ratio of these oxides is as follows: 5i (h 12-33 wt% Bt0320-35 wt% ZnO or SrO13-33 wt% CaOlO-2
5% by weight Zr0t 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 melt is poured into water, for example, and rapidly cooled 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 CaC01 (calcium carbonate), BzOi
(Boron oxide) is obtained by heat treatment of boric acid (HJOs), so CaCO3 and HtB (h) can be used in place of part or all of CaO and BzOi, respectively.The same applies to oxides of other components. It is.

In addition, 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,
It is preferable to use Ca, Srs Ba, and use one or more of these metal salts in combination.

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

The niobium and/or tantalum 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 temperature for this heat treatment is preferably 800°C to 1200°C, and if the temperature is outside this range, the resistance of the finished resistor will increase due to subtle fluctuations in the composition ratio caused by the working conditions of each step of processing the resistor material into an electrical resistor. It is difficult to stably obtain the desired resistance value, so it is desirable to use a non-oxidizing atmosphere for this heat treatment. Preferably, a mixed gas is used.

The composition ratio of each component of the resistor material is 50 to 95% by weight of niobium and/or tantalum molybdate, 4% by weight of glass powder, and 4% by weight of glass powder.
．． 5-49.5% by weight, alkaline earth metal fluoride 0.
5 to 25% by weight is preferred. Niobium and/or
Alternatively, if the amount of molybdate of tantalum is too small and the amount of glass is too large, the resistance value of the electrical resistor obtained by firing may become too high, which is undesirable. If the amount of glass 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 the circuit board. However, when the resistor is embedded in a laminated circuit board, the amount of niobium and/or tantalum 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 25% by weight, the temperature change coefficient of the finished electrical resistor will be greater than ±500 ppn+/''C, which is preferable. 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, turpentine oil, etc., and examples of the resin include cellulose derivatives such as ethyl cellulose and nitrocellulose, and other organic solvents. Examples include resin.

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 sheets include, for example, 35 to 45% by weight of aluminum oxide (AizOi), 25 to 35% by weight of silicon oxide (S10□), and boron oxide (B2(
h) 10-15% by weight, calcium oxide (Cab)
7-13% by weight, magnesium oxide (MgQ) 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 niobium and/or tantalum 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 includes:
It is composed of acrylic resins such as acrylic esters, resins such as polyvinyl butyral, plasticizers such as glycerin and diethyl phthalate, dispersants such as carboxylic acid salts, and solvents such as water and organic solvents.

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 Nt 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 manner as the resistor material paste coating. will be processed.

This base metal conductor material such as Nt 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 above-mentioned material is incorporated into the ceramic green sheet. A resistor material and a conductor material incorporated 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℃~1100℃
, 0.5 hours to 2 hours. As the non-oxidizing atmosphere, nitrogen gas and other active gases, as well as mixed gases containing these gases and hydrogen gas, can 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 less than ±500 ppm/''c, for example. This is because the resistor matches well with the conductor and the fired substrate, and because of the resistance of niobium and/or tantalum molybdates and alkaline earth metals. This is thought to be due to the unique moisture resistance of the resistor, which is made of a fired body of fluoride and glass, but the details are not clear. Alkaline earth metal fluorides can be recognized.

In the present invention, a molybdate of niobium and/or tantalum may be used as described above, but instead of this molybdate of niobium and/or tantalum, it becomes a molybdate of niobium and/or tantalum by heat treatment. It is also possible to use some or all of the precursors. In both of these cases, the mixture is mixed with glass and heat treated, then crushed.
Although it is preferable to use the material as a resistor material, this heat treatment is performed by applying a paste prepared by mixing it with the above-mentioned organic vehicle etc. to a green ceramic sheet, for example.
It is also possible to directly create a resistor by firing after heat treatment to remove organic matter.

In addition, the glass may be placed in a state where the mixed material of oxides constituting it is fired together with niobium and/or tantalum molybdate and alkaline earth metal fluoride, and these oxides A precursor of niobium and/or tantalum molybdate and/or its precursor, a part or all of this oxide together with a fluoride of an alkaline earth metal are made into a paste state as described above, and this is applied to a substrate. In the process of burning organic matter and subsequent calcination, it becomes a glass consisting of the above glass components, and this, niobium and/or tantalum molybdate and/or its precursor, and alkaline earth metal fluoride. Any material may be used as long as it can be fired to produce a resistor. For example, CaO (calcium oxide), which is a component of glass material, is Ca
Heating C0z (calcium carbonate), BzOs (boron oxide) is obtained from heating boric acid (HJ(h), so C
Ca in place of part or all of aO, B2O3, respectively
C0=, HzB (h can be used.The resistor material in the present invention is mainly composed of molybdate of niobium and/or tantalum, glass, and fluoride of alkaline earth metal as a result of the treatment process. It's fine as long as it's something you can do.

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%.

Each mixture of glass A and glass B was individually melted in an alumina crucible at 1400° C., and the melt was poured into water and rapidly cooled. Take out this quenched material, put it in a bot mill with ethanol, and use an alumina ball 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.

Niobium molybdate was also obtained from molybdenum oxide and niobium oxide.

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

(Margins below this page) When using 2C niobium molypde fi and fluoride together>
Table 2 (Continued) Each sample was heated at 1000°C in a gas atmosphere containing 98.5 vol% nitrogen (Nz) and 1.5 vol% hydrogen (H2).
The resultant was heat-treated for 1 hour, then ground with ethanol in a pot mill, and dried to obtain resistor material powder of less than 10 μl of heat-treated powder of glass, molybdate, and fluoride.

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, Al tax 40.0% by weight, SiO□35
．． To 100 parts by weight of ceramic raw powder consisting of 0% by weight, 13.0% by weight of n2oz, 07.0% by weight of Ca, and 5.0% by weight of MgO, 8 parts by weight of borivinyl butyral, 8 parts by weight of diethyl phthalate, and 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 were added and mixed in a ball mill to prepare a slurry. After defoaming treatment, a long ceramic green sheet with a thickness of 200 pm was prepared using a doctor blade method. was created. A green sheet piece with a length of 9 fins and a width of 9 m, and a green sheet piece with a length of 6 dragons and a width of 9 cranes were cut out from this ceramic green sheet.

Next, as shown in FIG. 1, 95 parts by weight of copper powder, 5 parts by weight of glass lift, 20 parts by weight of butyl calpitol as an organic vehicle, and ethyl cellulose were placed on the above-mentioned green sheet piece 1 measuring 9 vertical by 9 fl. 5 parts by weight were added, and the conductive material paste was mixed using a three-roll mill, and the conductive material paste was silk screen printed and dried at 125° C. for 10 minutes to form a thick conductive material coating 2.Next, the resistor obtained above was The material paste 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 top of the green sheet piece 1, the green sheet piece 4 having 6 cranes vertically and 9 fins horizontally obtained above is stacked as shown by the chain line in the figure.
The green sheet pieces 1.4, the conductor material coating 2, and the resistor material coating 3 are then heated at 400 to 500℃ in an oxidizing atmosphere such as air to form green sheet pieces 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, Nt 98.5v
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 fired sample No. 1) thus obtained was polished in the layer direction to expose the resistor layer,
This exposed resistor layer was analyzed by line diffraction (CuKα radiation), and the obtained results are shown in Figure 5. From this, it was possible to confirm the type of molybdate and the type of fluoride in the specimen. did it.

Next, the resistance value (R□) of this multilayer ceramic substrate 3a at 25°C and the resistance value (R,
□, ) was measured with a digital multimeter, and the temperature coefficient of resistance <TCR) was determined by the following formula.

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 size in Table 2. are shown in Table 3.

Example 2 A multilayer ceramic substrate was produced from the resistor materials shown in Table 4 in the same manner as in Example 1 except that tantalum molybdate was used instead of niobium molybdate.
As in Example 1, RlS, TCP, and resistance change rate were determined and are 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.
Table 5 shows the correspondence of O.

Example 3 A multilayer ceramic substrate was produced from the resistor materials shown in Table 6 in the same manner as in Example 1, except that a mixture of niobium molybdate and tantalum molybdate was used instead of niobium molybdate. However, as in Example 1, R
□, TCR5 resistance value change rate was determined and these are shown in Table 6.

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, R2, TCR, and resistance change rate were determined and shown in Table 7 in correspondence with the sample numbers.

Example 4 A multilayer ceramic substrate was produced from the resistor materials shown in Table 8 in the same manner as in Example 1, except that a molybdate shown in Table 8 in which part of the niobium in the niobium molybdate was replaced with tantalum was used. was prepared and R2 was prepared in the same manner as in Example 1.
,,TCP, and the rate of change in resistance value were determined and 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 did not contain alkaline earth metal fluoride, was used, and as in Example 1, Rzs, The TCR and resistance value change rate numbers were determined and shown in Table 9 in correspondence with the sample numbers.

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 except that no heat treatment was performed at 1000°C for 1 hour in a gas atmosphere containing 9B, 5vo1%, and hydrogen (Ih) 1.5vo1%. Similar to Example 1, Rts, T
CR and resistance change rate were 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.

(Space below this page) Table 3 (When fluoride is not used in combination with niobium molybdate) (Space below this page) Table 4 (When fluoride is used in combination with tantalum molybdate) (Continued) Table 5 (When fluoride is not added to the molybdenum shoulder of tantalum) Table 9 (When there is no fluoride in Table 716) Table 9 (When there is no fluoride in Table 3) Comparative example 1 (MoSi2-TaSiz glass Resistor material) A mixture of 16 parts by weight of MoSiz and 9 parts by weight of Ta5iz was heated in the air at 1400°C, and the product was ground with ethanol in an alumina ball in a bot mill for 24 hours, and dried to obtain a fine powder of 10 μm or less. Ta. BaOs Bz
75 parts by weight of a glass lift consisting of O, MgO, CaO, and SiO□ and 25 parts by weight of an organic vehicle (20 parts by weight of butyl calpitol, 5 parts by weight of ethyl cellulose) are mixed in a roll mill to form a resistor material paste. I got it.

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, the ceramic green sheet was coated with a resistor material coating, heat-treated to remove organic matter, and then fired simultaneously. As shown in Figure 3, warpage is observed,
In addition, the decomposition reaction of Mo5iz and TaSi generated Sin and gas, causing blistering as shown in FIG. 4, making it impossible to put it to practical use. Note that lla is the ceramic layer 1as, 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 (MoSiz-BaFz glass-based resistance material antibody material Siz 70 parts by weight, 8aFz 20 parts by weight,
iOts Zn.

After mixing 10 parts by weight of a glass lift consisting of ZrO, Ca0z, Alt(h) in a ball mill and heat-treating the obtained powder at 1200°C in an argon (Ar) gas atmosphere, it was mixed with ethanol in a bot mill. It was ground with an alumina ball for 24 hours and dried to obtain a fine powder of 10 μm or less.

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

Table 11 shows the Rzs, TCR, 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.

Table 11 From the above results, all of 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 when the resistor material is heat-treated. In contrast, the multilayer ceramic substrate of Comparative Example 1 shows warpage, and the multilayer ceramic substrate of Comparative fH2 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 niobium and/or tantalum 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 by, for example, ±
It can be reduced to 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.

In addition, by heat treating niobium and/or tantalum 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, 1932 Figure 1 Figure 3 Figure 4 Figure 5 X-ray diffraction diagram 20 Gieg)

Claims (5)

[Claims] (1) Niobium and/or tantalum molybdate;
An electrical resistor characterized by having a fired body containing an alkaline earth metal fluoride. (2) The fired body is fired from a resistor material containing at least one of niobium and/or tantalum molybdate and its precursor, and an alkaline earth metal fluoride as a main component. An electrical resistor according to claim 1. (3) The main component of the resistor material is 50 to 95% by weight of at least one of niobium and/or tantalum molybdate and its precursor in terms of the niobium and/or tantalum molybdate; 0.5-25% by weight of alkaline earth metal fluoride and 4.5-49.5% by weight of glass
An electrical resistor according to claim 2, characterized in that it consists of: (4) Heat-treating a resistor material containing at least one of molybdates of niobium and/or tantalum and their precursors as main components and fluorides of alkaline earth metals as main components; An electric resistor characterized in that the obtained resistor material is fired to obtain an electric resistor comprising a fired body containing niobium and/or tantalum molybdate and alkaline earth metal fluoride. Production method. (5) The main component of the resistor material before heat treatment is niobium and/or tantalum molybdate and at least one of its precursors, which weighs 50 to 95% in terms of the niobium and/or tantalum molybdate. %, alkaline earth metal fluoride 0.5-25% by weight, glass 4.5-49%
．． 5. The method of manufacturing an electrical resistor according to claim 4, wherein the content is 5% by weight.