JPH0469588B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a thick film type electrical resistor provided on a fixed chip resistor or a circuit wiring board, etc., particularly an electrical resistor that can be obtained by firing in a non-oxidizing atmosphere, and the like. Regarding the manufacturing method. BACKGROUND 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 ceramic chip. There is also a fixed chip resistor in which the thick film resistor is formed so as to span both electrodes. Conventionally, in order to install such a thick film resistor on a circuit board, a conductive material paste such as Ag or Ag-Pd is applied to the surface of an alumina substrate obtained by baking at around 1500℃, and after baking, ,for example
A paste containing RuO ₂ as a resistor material is applied by screen printing, and then heated at 750 to 850℃.
The common method is to bake the resistor in a wafer, and then adjust the resistance value by trimming, etc., if necessary. However, in recent years, frivolous and
The demand for shorter, smaller, and lower costs is becoming stronger, and studies are being conducted to further reduce the size and cost of circuit boards. For the former, specific measures for downsizing include:
Firstly, circuit boards are becoming more multi-layered, and secondly, resistors are being built internally. As an example of multilayering a circuit board, ceramic green sheets (raw sheets) printed with a conductive material paste such as Ag or Ag-Pd are laminated and pressed together, and then simultaneously fired in the atmosphere at 800 to 1100℃. Examples include multilayer wiring boards,
In addition, as an example of internally incorporating a resistor, a _RuO2 -based resistor material paste is further printed on a ceramic green sheet printed with the conductor material paste, laminated and crimped in the same manner as above, and then co-fired. The resulting resistor-incorporated multilayer wiring board and the like are known. In addition, as a specific measure to reduce the cost of the latter, we will use inexpensive Ni to replace expensive noble metal conductor materials such as Ag or Ag-Pd materials.
Alternatively, base metal-based conductive materials such as Cu are used, and they are heated at 800°C in a neutral or reducing non-oxidizing atmosphere such as nitrogen gas or hydrogen-containing nitrogen gas to avoid high resistance due to oxidation. A multilayer wiring board obtained by co-firing with green ceramic at ~1100℃ has been put into practical use. Furthermore, as described in JP-A No. 56-153702, a resistor material made of MoSi ₂ -TaSi ₂ and glass is coated on an alumina substrate having a copper (Cu) conductor and heat-treated. Thick 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, RuO ₂ -based resistor materials have been co-fired with green ceramics in nitrogen gas or hydrogen-containing nitrogen gas atmospheres. Sometimes 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 MoSi ₂ - TaSi ₂ 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 There is a problem that gas is generated due to the decomposition reaction of ₂ -TaSi ₂ , which tends to cause blisters in the fired product. In order to improve this, as described in JP-A-60-198703, there is a known example in which a resistor material made of MoSi ₂ -metal fluoride (e.g. calcium fluoride) and glass is used. There is no warping or blistering during firing as mentioned above. However, when a thick film resistor obtained by applying this MoSi ₂ -metal fluoride and glass resistor material to a green ceramic sheet and simultaneously firing the resistor material, the resistor material obtained by coating the resistor material made of MoSi 2 -metal fluoride and glass for 1000 hours in 95% relative humidity has a
A 10% increase in resistance value was observed, and the resistor could no longer perform its intended function. Furthermore, the above-mentioned conventional electrical 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, an electrical resistor obtained by firing a resistor material mainly composed of a metal salt of molybdate and glass, and a metal fluoride further contained in this resistor material were proposed. We proposed electrical resistors obtained by firing resistor materials, and even when they were incorporated into multilayer substrates, the fired products did not warp, bulge, or change in resistance as described above, and furthermore, the latter's electrical resistance The body was able to make the temperature change coefficient of resistance smaller than the former. 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-mentioned problems, the present invention provides at least one of zirconium and/or hafnium molybdates and their precursors, an alkaline earth metal fluoride, The present invention provides an electrical resistor paste characterized by containing an alkaline earth metal carbonate. Further, the present invention has zirconium and/or zirconium as the main component.
or at least one of hafnium molybdate and its precursor, an alkaline earth metal fluoride, and an alkaline earth metal carbonate, the zirconium and/or hafnium molybdate and its precursor; At least one type of body
A mixture system of alkaline earth metal fluorides was heat-treated, and the above-mentioned alkaline earth metal carbonate was added to the material obtained by this heat treatment to constitute a resistor material, and this resistor material was used to make a paste. The present invention provides a method for producing an electrical resistor paste characterized by the following. Next, the present invention will be explained in detail. The molybdate of zirconium and/or hafnium in the present invention includes, for example, ZrMo ₂ O ₈ ,
Examples include a single substance such as HfMo ₂ O ₈ or a mixture thereof. Furthermore, molybdates consisting of a plurality of these metals can also be used, such as (Nb _x Ta _y ) Mo ₃ O ₁₄ where x+y=1, etc., which may be used singly or in combination, and each of the above-mentioned individual substances, Used by mixing with mixed substances. Such molybdates of zirconium and/or hafnium can be synthesized by heat treatment of the respective metal oxides and molybdenum oxide (MoO ₃ ), but they can also be synthesized by heat treatment using their precursors. You can also. In the present invention, it is preferable to use a binder, and examples thereof include glass, and this glass may be a commonly known glass, and is not limited to a glass with a specific composition, but may include Pb ₃ Oxides such as O ₄ , Bi ₂ O ₃ , SnO ₂ , and CdO may be reduced and metalized when resistor materials containing them are fired in a non-oxidizing atmosphere, and these metals are If it is undesirable for this to occur, it is preferable not to contain these oxides since they change the value. Glass components include SiO ₂ , B ₂ O ₃ , ZnO,
CaO, SrO, ZrO2, _etc. are preferred, and the composition ratio of these oxides is: _SiO2 12-33% by weight _{B2O3 20-35} % by weight ZnO or SrO 13-33% by weight CaO 10-25% by weight ZrO ₂ 15 to 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. Put this mixture into a crucible,
After melting at a temperature of 1200 to 1500°C, 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 replaced by CaCO ₃ (calcium carbonate), B ₂ O ₃ (boron oxide) is replaced by boric acid (H ₃
BO ₃ ), so CaO, B ₂
each in place of part or all of O ₃
CaCO ₃ and H ₂ BO ₃ can be used. The same applies to oxides of other components. In addition, the alkaline earth metal fluoride used in the present invention is represented by the general formula MeF ₂ when Me is a metal, and Me is an alkaline earth metal,
That is, it is preferable to use Mg, Ca, Sr, and Ba, and 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. Zirconium obtained as described above and/or
Alternatively, hafnium molybdate, glass powder, and fluorides such as alkaline earth metals may be mixed together and used as resistor materials as they are, but it is better to heat-treat and pulverize them to use as resistor materials. This is preferable in view of the resistance temperature characteristics of the resistor obtained by firing. The heat treatment temperature is 800℃~
A temperature of 1200°C is preferable; if it is outside this range, the resistance value of the finished resistor will be easily affected by slight variations in the composition ratio due to 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. This heat treatment is preferably performed in a non-oxidizing atmosphere, and it is preferable to use not only nitrogen gas or other inert gas, but also a mixed gas containing hydrogen gas. In order to create a resistor for a fixed resistor or a thick film resistor from the resistor material powder thus obtained, the resistor material powder is applied to, for example, a ceramic green sheet. To carry out this application, a vehicle is mixed with these resistor material powders to enable silk screen printing, for example, and at this time, a coating liquid is prepared to which a carbonate of an alkaline earth metal is added. Examples of this carbonate include those having the general formula Me′CO ₃ , and Me′ is preferably an alkaline earth metal such as Mg, Ca, Sr, or Ba, but is not limited to these and may also include other metal carbonates. used. The composition ratio of each component of the resistor material is 45 to 95% by weight of zirconium and/or hafnium molybdate, 4 to 54% by weight of glass powder, 0.5 to 20% by weight of alkaline earth metal fluoride, and alkaline earth metal fluoride. 0.5-50% by weight of metal carbonate 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 electrical resistor obtained by firing may become too high, which is undesirable. And/or 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 the circuit board.
However, when the resistor is embedded in a laminated circuit board, the amount of molybdate of zirconium and/or hafnium may be greater than the above range, and no glass may be included. Also, if the alkaline earth metal fluoride is less than 0.5% by weight or more than 20% by weight, the temperature change coefficient of the finished electrical resistor will be greater than ±300ppm/℃, which is not desirable. There is. However, materials outside this range can also be used as long as the temperature change coefficient of resistance is improved. The vehicle for the coating liquid is preferably one that can be burned out in the pre-baking stage.For this purpose, the resin is dissolved or dispersed in an organic vehicle, that is, an organic solvent, and various types of plasticizers, dispersants, etc. are added as necessary. Preferably, additives are added. 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 resins. The ratio of the organic vehicle to the resistor material powder varies depending on the organic solvent, resin, etc. used, but the ratio of the organic solvent to the resin is 20 to 50.
The latter is preferably 80 to 50% by weight. 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 board and further processed as described below to create a resistor.This board is coated with a ceramic green sheet that is fired together with the 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 coated on the ceramic green sheet, and then fired. These can also be applied when forming a laminate. The ceramic green sheet includes, for example, 35 to 45% by weight of aluminum oxide (A ₂ O ₃ );
Silicon oxide ( _SiO2 ) 25-35% by weight, boron oxide ( _B2
O ₃ ) 10-15% by weight, calcium oxide (CaO) 7
~13% by weight, magnesium oxide (MgO) 7-10
For example, a slurry prepared by mixing a mixture of oxides of ceramic constituents such as % by weight 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 preferably applied to a ceramic green sheet by means such as silk screen printing, dried, and then heat treated at 400 to 500°C to decompose and burn the resin components. 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, and the paste is also applied to the ceramic green sheet in the same way as the resistor material paste coating. will be processed. Examples of paste compositions of base metal conductor materials such as Ni or Cu or noble metal conductor materials such as Ag or Ag-Pd include those in which 2 to 15 weight % of glass frit is added 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 used, and in the case of a thick film resistor of a multilayer board, the resistor material and conductor material incorporated in the unfired state are further laminated to form a predetermined circuit. It is 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°C to 1100°C for 0.5 hours to 2 hours. As the non-oxidizing atmosphere, nitrogen gas, other inert gases, and mixed gases containing these gases and hydrogen gas may also be used. Furthermore, when using a noble metal conductor material such as Ag or Ag-Pd, it can also be fired in an oxidizing atmosphere such as air. As described above, a circuit wiring board incorporating a conductor and/or a resistor is completed, but there may be cracks, distortions, etc. between the fired board and the resistor as well as between the fired board and the resistor due to firing. In addition to not causing blistering, the resistor can be placed in a high humidity atmosphere.
Even if it is left unused for more than 1000 hours, its resistance value can be suppressed to change within ±2%, ensuring high reliability, and the temperature change coefficient of resistance value can also be kept below ±300ppm/℃, for example. can.
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 earth metal fluoride, and glass. It is thought that this is the case, but the details are not clear. Note that zirconium and/or hafnium molybdate and alkaline earth metal fluoride can be found in the resistor by X-ray diffraction analysis. In the present invention, zirconium and/or hafnium molybdate may be used as described above, but instead, a part or all of a precursor that becomes zirconium and/or hafnium molybdate through heat treatment may also be used. can. 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. However, a paste made by mixing it with the above-mentioned organic vehicle, etc. without performing this heat treatment can be used, for example, as a green ceramic sheet. It is also possible to directly create a resistor by coating the material on the surface of the material, 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 the oxides constituting it is fired together with molybdates of diumconium and/or hafnium and fluorides of alkaline earth metals, 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 the substrate. In the process of combustion of organic matter and subsequent firing, a glass consisting of the above glass components is formed, and this is combined with zirconium and/or hafnium molybdate and/or its precursor, alkaline earth metal fluoride and Any material that can produce a resistor by firing with an alkaline earth metal carbonate (or a heating element thereof) may be used. For example, CaO (calcium oxide), which is a component of glass materials, can be obtained by heating CaCO ₃ (calcium carbonate), and B ₂ O ₃ (boron oxide) can be obtained by heating boric acid (H ₂ BO ₃ ), so CaO, CaCO ₃ and H ₂ BO ₃ can be used in place of part or all of B ₂ O ₃ . 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. Examples Next, examples of the present invention will be described. Example 1 Each component was weighed and mixed to have the composition shown in Table 1 in terms of oxide.

[Table] In the table, the unit is weight%. Each of the mixtures of Glass A and Glass B was individually melted at 1400° C. in an alumina crucible, and the melt was poured into water and rapidly cooled. This quenched material was taken out and placed in a pot mill with ethanol, and ground with an alumina ball for 24 hours to a particle size of 10 μm.
The following glass powder was obtained. 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 alkaline earth metal fluoride obtained above are shown in Table 2.
They were weighed and mixed in the proportions shown below.

【table】

[Table] Each sample was heat-treated at 1000°C for 1 hour in a gas atmosphere containing 98.5 vol% nitrogen (N ₂ ) and 1.5 vol% hydrogen (H ₂ ), then ground with ethanol in a pot mill, and dried. Resistor material powders of glass, molybdate, and fluoride heat-treated powders of less than 10 μm were obtained. Next, carbonates of alkaline earth metals were mixed with each sample in the proportions shown in the table, and after this mixing, 100 parts by weight of the resistor material powder was mixed with an organic vehicle (90 parts by weight of butyl carbitol, 10 parts by weight of ethyl cellulose). 25 parts by weight were added and mixed in a roll mill to obtain a resistor material paste. On the other hand, A ₂ O ₃ 40.0% by weight, SiO ₂ 35.0% by weight,
B ₂ O ₃ 13.0% by weight, CaO 7.0% by weight, MgO 5.0% by weight
100 parts by weight of ceramic raw material powder consisting of 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 were added and mixed in a ball mill to prepare a slurry. After defoaming, a long ceramic green sheet with a thickness of 200 μm was prepared by a doctor blade method. A green sheet piece measuring 9 mm in length and 9 mm in width and another green sheet piece measuring 6 mm in length and 9 mm in width were cut out from this ceramic green sheet. Next, as shown in Fig. 1, 20 parts by weight of butyl carbitol and 5 parts by weight of ethyl cellulose were added as an organic vehicle to 95 parts by weight of copper powder and 5 parts by weight of glass frit on the green sheet piece 1 measuring 9 mm in length and 9 mm in width. A conductor material paste obtained by mixing these materials 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 the green sheet piece 1, the length 6 mm obtained above was
Green sheet pieces 4 with a width of 9 mm are stacked as shown by the chain lines in the figure, and thermocompression bonded at 100° C. and 150 kg/cm ² . Next, this is heated at 400 to 500℃ in an oxidizing atmosphere such as air.
The remaining organic matter in each of the green sheet pieces 1 and 4, the conductor material coating 2, and the resistor material coating 3 is decomposed and burned. After removing organic matter in this way, _N2
In a mixed gas of 98.5vol% and H ₂ 1.5vol%, at 950℃,
After firing for 1 hour, as shown in FIG. 2, a thick film conductor of the fired conductive material coating film 2 is formed between the porcelain layer 1a of the fired body of the green sheet piece 1 and the porcelain layer 4a of the fired body of the green sheet piece 4. 2a, a multilayer ceramic substrate having a thick film resistor 3a of the fired body of the resistor material coating 3 was completed. This multilayer board includes a third
No warping or blistering as shown in Figures 4 and 4 was observed. The multilayer ceramic substrate of the fired body (sample No. 1) thus obtained was polished in the layer direction to expose the resistor layer, and the exposed resistor layer was analyzed by X-ray diffraction (CuKα rays). The results are shown in the fifth column.
As shown in the figure. As a result, the type of molybdate and the type of fluoride in the specimen could be confirmed as shown in the figure. Next, the resistance value (R ₂₅ ) of this multilayer ceramic substrate 3a at 25°C and the resistance value (R ₁₂₅ ) when heated to 125°C were measured with a digital multimeter.
The temperature coefficient of resistance (TCR) was calculated using the following formula. TCR=R ₁₂₅ −R ₂₅ /R ₂₅ ×10000 (ppm/°C) Table 3 shows the measured resistance value of R ₂₅ and the calculated value of TCR. In addition, the multilayer ceramic substrate obtained above was
After being left for 1000 hours at ℃, 95% relative humidity
Table 3 shows the results of measuring the resistance value at 25°C and determining the rate of change. In addition, electrical resistors made in the same manner as in Example 1 from each sample No. except for carbonates of alkaline earth metals and samples from which fluorides of alkaline earth metals were removed. Each was measured in the same manner as above, and the obtained results are shown in Sample No. 2 in Table 2.
The corresponding values 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 hafnium molybdate was used instead of zirconium molybdate. Find R ₂₅ , TCR, and rate of change in resistance value and list them in Table 5.
The corresponding sample numbers are shown. In addition, a multilayer ceramic substrate was fabricated using a resistor sample from which the alkaline earth metal carbonate was removed and a resistor material from which the alkaline earth metal fluoride was removed, and measurements were performed in the same manner as above. The measured values and calculated values are shown in Table 5 in correspondence with the sample numbers in the same way as above. Example 3 A multilayer ceramic substrate was made from the resistor materials shown in Table 6 in the same manner as in Example 1, except that the molybdate shown in Table 6 in which multiple metal atoms were substituted was used instead of the zirconium molybdate. The R ₂₅ , TCR, and resistance change rate were determined in the same manner as in Example 1, and these are shown in Table 7. As in the previous example, resistor materials containing no alkaline earth metal carbonates and resistor materials containing no alkaline earth metal fluorides were used as the samples in Table 6.
A multilayer ceramic substrate was prepared in the same manner as in Example ₁ , except that it was prepared according to the sample No. The results are shown in Table 7. Example 4 A multilayer ceramic substrate was fabricated from the resistor materials shown in Table 8 in the same manner as in Example 1, except that a mixture of two types of molybdate of zirconium and hafnium was used instead of molybdate of zirconium. , R ₂₅ , TCR, and resistance change rate were determined in the same manner as in Example 1, and these are shown in Table 9. In addition, as in the previous example, the characteristic values obtained in the same manner as above for a resistor material that does not contain alkaline earth metal carbonate and also for a resistor material that does not contain alkaline earth metal fluoride are sample No. are shown in Table 9 in correspondence. Example 7 In Example 1, the mixture of molybdate, alkaline earth metal fluoride, and glass powder was heated at 1000°C in a gas atmosphere of 98.5 vol% nitrogen (N ₂ ) and 1.5 vol% hydrogen (H ₂ ). Multilayer ceramic substrates were prepared from the resistor materials shown in Table 10 in the same manner except that the 1-hour heat treatment was not performed, and the R ₂₅ , TCR, and resistance change rate were determined in the same manner as in Example 1 and are shown in Table 11. 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】

【table】

【table】

【table】

【table】

【table】

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【table】

[Table] Comparative Example 1 (MoSi ₂ - TaSi ₂ glass-based resistor material) A mixture of 16 parts by weight of MoSi ₂ and 9 parts by weight of TaSi ₂ was heated in air at 1400°C, and the product was mixed with ethanol in an alumina ball in a pot mill. It was ground for 24 hours and dried to obtain a fine powder of 10 μm or less. For 25 parts by weight of the fine powder thus obtained, BaO,
75 parts by weight of glass frit consisting of B ₂ O ₃ , MgO, CaO, SiO ₂ and 25 parts by weight of an organic vehicle (20 parts by weight of butyl carbitol, 5 parts by weight of ethyl cellulose) were added and 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, we formed a resistor material coating on a ceramic green sheet, heat-treated it to remove organic matter, and then fired it simultaneously. As shown in Figure 3, warpage is observed, and MoSi ₂ ,
Due to the generation of SiO ₂ gas during the decomposition reaction of TaSi, blistering occurred as shown in Figure 4, making it impossible to put it to practical use. Note that 11a 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 ₂ -BaF ₂ glass-based resistor material) 70 parts by weight of MoSi ₂ , 20 parts by weight of BaF ₂ , SiO ₂ ,
10 parts by weight of glass frit consisting of Zn, ZrO ₂ , CaO ₂ and A ₂ O ₃ were mixed in a ball mill, the resulting powder was heat treated at 1200°C in an argon (Ar) gas atmosphere, and then mixed with ethanol in a pot mill. Grind with alumina ball for 24 hours and dry
A fine powder of 10 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 15 shows the R ₂₅ , 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] 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 ±300 ppm / ℃, the multilayer ceramic substrate of Comparative Example 1 shows warping and blistering, 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 than the TCR.
It can be seen that this is an order of magnitude larger. Effects of the Invention According to the present invention, it is possible to provide a resistor paste containing a molybdate of zirconium and/or hafnium, a fluoride of an alkaline earth metal, and a carbonate of an alkaline earth metal. For example, if a resistor is formed by firing a ceramic green sheet together with a base metal conductor material in a non-oxidizing atmosphere, the fired body will not warp or bulge due to firing, and the resistor will not warp or bulge. Not only can the temperature change be reduced, but the temperature change coefficient of the resistance value of the resistor can be, for example, ±300 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 also to provide excellent electronic components for electronic devices that require particularly precise operation. I can do it. Furthermore, when heat treating zirconium and/or hafnium molybdates, alkaline earth metal fluorides, and glass, for example, the absolute value of the temperature change coefficient of the resistor can be reduced compared to those that are not treated, resulting in excellent characteristics. can provide resistors of

[Brief explanation of the drawing]

Fig. 1 is a diagram showing an example of a state in which a resistor material coating film and a conductor 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 and 4 are green sheet pieces, 2 is a conductor 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.

Claims (1)

[Claims] 1. It is characterized by containing at least one of zirconium and/or hafnium molybdate and its precursor, an alkaline earth metal fluoride, and an alkaline earth metal carbonate. electrical resistor paste. 2 The main components are 45 to 95% by weight of at least one of molybdates of zirconium and/or hafnium and their precursors, calculated as molybdates of zirconium and/or hafnium, and molybdates of alkaline earth metals. The electric resistor paste according to claim 1, characterized in that it consists of 0.5 to 20% by weight of a compound, 0.5 to 50% by weight of an alkaline earth metal carbonate, and 4 to 54% by weight of glass. 3 Containing as a main component at least one of zirconium and/or hafnium molybdate and its precursor, an alkaline earth metal fluoride, and an alkaline earth metal carbonate, and the zirconium and/or hafnium A resistor is prepared by heat-treating a mixture system of molybdate and at least one of its precursors and an alkaline earth metal fluoride, and adding the alkaline earth metal carbonate to the material obtained by this heat treatment. 1. A method for producing an electrical resistor paste, characterized in that the resistor material is made into a paste. 4. The main component of the resistor material before heat treatment is 45 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 fluorides
0.5 to 20% by weight, 4 to 54% by weight of glass, and 0.5 to 50% by weight of alkaline earth metal carbonate,
4. The method for producing an electrical resistor paste according to claim 3, wherein the mixture system of the three main components excluding 0.5 to 50% by weight of the alkaline earth metal carbonate is heat-treated.