JPH0477445B2 - - 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., which can be obtained by firing in a non-oxidizing atmosphere, and which has high durability. The present invention relates to an electrical resistor with improved power operation change rate and withstand voltage characteristics, and a method of manufacturing the same. 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 are also fixed chip resistors 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, etc., and then heated at 750 to 850℃.
A common method is to bake the resistor with a wafer, and then adjust the resistance value by trimming or the like as necessary. However, in recent years, frivolous and
The demand for shorter, smaller, and lower costs is becoming stronger, and studies are also being conducted to further reduce the size and cost of circuit boards. As a concrete measure for miniaturization of the former,
Firstly, circuit boards are becoming more multi-layered, and secondly, resistors are being built internally. An example of multi-layered circuit boards is obtained by laminating and pressing ceramic green sheets (raw sheets) printed with conductive material paste such as Ag or Ag-Pd, and then simultaneously firing them in the atmosphere at 800-1100℃. 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 misalignment due to the difference in 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, an example is known in which a resistor material made of MoSi ₂ -metal fluoride (e.g. potassium fluoride) and glass is used, as described in JP-A-60-198703. There is no warping or blistering during firing as mentioned above. However, a thick film resistor obtained by coating a resistor material made of MoSi ₂ -metal fluoride and glass on a green ceramic sheet and co-firing it is 95%
When left in relative humidity for 1000 hours, the resistance value increases by 5 to 10%, making it impossible to perform the intended function as a resistor. Therefore, the present inventors developed molybdic acid, an alkaline earth metal that can be obtained by firing at 800 to 1100°C in a non-oxidizing atmosphere, along with ceramic green sheets printed with base metal conductor pastes such as Cu and Ni. A thick film resistor containing salt was proposed.
This is preferable because almost no increase in resistance value is observed even when left for a long time under high humidity as described above. However, when a thick film resistor containing molybdate of an alkaline earth metal is subjected to a cycle of turning on the rated voltage for 1.5 hours and turning it off for 0.5 hours in an atmosphere of 40 ± 2 degrees Celsius and a relative humidity of 90 to 95%, When time is added, there is a change in resistance value of ±3%≦ (absolute value is greater than 3), and the voltage resistance in the humidity load test is
In other words, there was a problem with durability. In addition, even without such high humidity, this thick film resistor can be tested for voltage operation for 240 ^+8/-0 hours at 70±5℃ with the rated voltage turned on for 1.5 hours and turned off for 0.5 hours. When this was done, there was a problem that the resistance value changed by less than ±2%, and the power operation changed greatly. In addition, devices and circuit boards on which thick-film resistors containing molybdate of alkaline earth metals are formed, or electronic devices mounted with these devices and circuit boards, must be handled under conditions of low temperature and low humidity. Then, high-voltage static electricity generated by friction between these elements or the friction of the clothes of the workers handling these elements or equipment will be applied to the thick film resistor, and the resistance value of this resistor will decrease. There is a problem in that it significantly reduces the This decrease in resistance value is 20~
Once the resistance value has decreased by as much as 50%, it does not return to its original resistance value, and there has been a desire to improve its voltage resistance. Therefore, the first 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 conductive materials and incorporated into multilayer boards. Another object of the present invention is to provide an electrical resistor whose resistance value is stable even if it is left for a long time under high humidity. A second object of the present invention is to provide an electrical resistor having excellent characteristics that can also be obtained by firing the resistor material in a reducing atmosphere. A third object of the present invention is to provide an electrical resistor with improved durability. A fourth object of the present invention is to provide an electrical resistor that satisfies both the miniaturization of circuit boards and cost reduction. A fifth object of the present invention is to provide a manufacturing method that can further improve the characteristics of the electrical resistor. A sixth object of the present invention is to provide a voltage-resistant electrical resistor that achieves the above objects and does not impair its function as a resistor even when a high voltage is applied. A seventh object of the present invention is to provide an electrical resistor that achieves the above objects and has a small rate of change in power operation. Means for Solving the Problems In order to achieve the above object, the present invention provides an alkaline earth metal molybdate, Au, Ag, Pt,
The present invention provides an electrical resistor characterized by having a fired body containing at least one metal selected from the group of Ru, Ni, Cu, Co, and Pd and/or its metal oxide. The electrical resistor is fired from a resistor material containing as main components at least one molybdate of an alkaline earth metal and its precursor, and a metal in the group such as Au and/or its metal oxide. In particular, it is preferable that the main component of this resistor material is at least one of an alkaline earth metal molybdate and a precursor thereof.
A composition comprising 30 to 96% by weight of seeds in terms of molybdate of the alkaline earth metal and 4 to 70% by weight of glass, based on 100 parts by weight of the composition.
It is preferable to contain 0.05 to 3.00 parts by weight of a metal from the group such as Au and/or its metal oxide. Further, it has a lumpy particle, an acicular particle attached to the lumpy particle or existing in the vicinity of the lumpy particle, and a glass layer, and contains a metal in the group such as Au and/or its metal oxide. The present invention provides an electrical resistor which is a fired body, wherein the lumpy particles contain a molybdate of an alkaline earth metal, and the acicular particles contain a reduction product of the molybdate. Preferably, the acicular particles are a reduction product produced by reducing the surface of the bulk particles. In addition, molybdates of alkaline earth metals,
The present invention provides an electric resistor characterized by having a fired body containing a metal in the group such as Au and/or its metal oxide, and titanium oxide, and the fired body of this electric resistor is At least one of an alkaline earth metal molybdate and a precursor thereof
It is preferable that the resistor material is fired from a resistor material containing as main components a seed, a metal from the group such as Au and/or its metal oxide, and titanium oxide. In addition, molybdates of alkaline earth metals,
A metal from the above group such as Au and/or its metal oxide, Y, La, Ce, Pr, Nd, Sm, Eu, Gd,
Provided is an electrical resistor characterized by having a fired body containing an oxide of at least one element selected from the group of Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, and Pm. The fired body of the electrical resistor contains at least one molybdate of an alkaline earth metal and its precursor, a metal from the group such as Au and/or its metal oxide, Y, La,
Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho,
It is preferable that the resistor material is fired from a resistor material containing as a main component an oxide of at least one element selected from the group of Er, Tm, Yb, Lu, Sc, and Pm. In addition, molybdates of alkaline earth metals,
A metal in the group such as Au and/or its metal oxide, titanium oxide, Y, La, Ce, Pr, Nd,
Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,
The present invention provides an electrical resistor characterized by having a fired body containing an oxide of at least one element selected from the group of Lu, Sc, and Pm, the fired body containing molybdic acid of an alkaline earth metal. At least one salt and its precursor, a metal from the group such as Au and/or its metal oxide, titanium oxide, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb ,
It is preferable that the resistor material is fired from a resistor material containing as a main component an oxide of at least one element selected from the group of Dy, Ho, Er, Tm, Yb, Lu, Sc, and Pm. Further, heat treating a resistor material containing at least one of molybdates of alkaline earth metals and their precursors as main components, and metals in the group such as Au and/or metal oxides thereof, The resistor material obtained by this heat treatment is fired, and the electrical resistance is made of a fired body containing an alkaline earth metal molybdate and a metal from the above group such as Au and/or its metal oxide. The present invention provides a method for producing an electrical resistor, characterized in that the main component of the resistor material before heat treatment is at least one of an alkaline earth metal molybdate and its precursor. 30 to 96% by weight calculated as the molybdate of the alkaline earth metal, and 4 to 70% by weight of the glass.
% by weight, and 0.05 to 3.00 parts by weight of a metal in the group such as Au and/or its metal oxide based on 100 parts by weight of the composition. Next, the present invention will be explained in detail. For example, as shown in FIG.
A structure in which acicular particles are dispersed is exemplified, and in this example, acicular particles are attached to spherical particles or exist in the vicinity thereof. Such a structure allows electrical current to flow through spherical particles and needle-like particles that are in contact with or in close proximity. Such a structure can be formed, for example, by firing bulk particles of the resistor material and growing a product on the surface into a needle shape, which will be described in detail later. Molybdate of an alkaline earth metal can be used as such a resistor material, but if Me is an alkaline earth metal, the general formula MeMoO ₄ is used.
Me ₃ MoO ₆ , Me ₂ MoO ₅ , Me ₂ Mo ₇ , MeMo ₄ O ₁₃ ,
_{MeMo7O24 , MeMo3O10 , Me2MoO5 , Me2Mo3 _}
Those represented by O ₁₁ etc. are preferred. in particular,
For example, MgMoO ₄ , CaMoO ₄ , SrMoO ₄ ,
_BaMoO4 , _{BaMo2O7 , BaMo4O13 , BaMo7O24 ,
BaMo3O10 , Ca3MoO6 , Sr3MoO6 , Ba3MoO6 ,}
Examples include Ba ₂ MoO ₅ and Mg ₂ Mo ₃ O ₁₁ . Further, the following complex molybdates are also exemplified. (Mgx Cay)MoO ₄ , where x+y=1, (Cax Sry)MoO ₄ , where x+y=1, (Mgx Bay)MoO ₄ , where x+y=1, (Max Cay Baz)MoO ₄ , where x+y+z =
1. (Cax Sry Baz)MoO ₄ , however, x+y+z=
1. (Mgx Cay Srz Baw) MoO ₄ , however, x+Y+z
+z=1, (Cax Sry)MoO ₆ , where x+y=3, (Srx Bay)MoO ₆ , where x+y=3. Such molybdates of alkaline earth metals are It can be synthesized by mixing a substance serving as a metal oxide precursor and molybdenum oxide (MoO ₃ ) or its precursor at a predetermined molar ratio and heat-treating the mixture. For example, calcium carbonate (CaCO ₃ ) is a precursor of CaO.
Alternatively, calcium hydroxide (Ca(OH) ₂ ) and molybdenum oxide (MoO ₃ ) or its precursor, such as molybdic acid (H ₂ MoO ₄ ), are mixed in a predetermined molar ratio and heat treated. The heat treatment conditions at this time include 600 to 1000°C for 1 to 3 hours. In addition, alkaline earth metal molybdates are
It can also be synthesized by heat treatment of alkaline earth metal oxides and molybdenum oxide (MoO ₃ ). For example, calcium molybdate is synthesized by heat-treating CaO and MoO ₃ , but in this case, since MoO ₃ tends to sublime, it is preferable to heat-treat while applying pressure. The same applies to other alkali metals. In addition, in the present invention, for example, Au, Ag, Pt, Ru,
At least one metal selected from the group of Ni, Cu, Co, and Pd and/or its metal oxide is used. Examples of this metal oxide include Pdo,
Examples include NiO, CoO, RuO ₂ , CuO, and the like. These metals and metal oxides may be used alone or in combination. The metal oxide is reduced by being fired in a reducing atmosphere. In addition, Y, La, Ce, Pr, used in the present invention,
Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,
Oxygen compounds of the elements Yb, Lu, Sc, and Pm are oxides of Sc, Y, and lanthanoids (element numbers 57 to 71) belonging to subgroup a of the periodic table, and these rare earth elements are divalent and tetravalent. Compounds with oxidation numbers such as oxidation numbers are also produced, but oxides with trivalent oxidation numbers are generally stable and are preferably used. Furthermore, titanium oxide used in the present invention is represented by the general formula TixOy, and specifically includes TiO, Ti ₂ O ₃ ,
TiO ₂ etc. are preferred. In the present invention, it is preferable to use glass, and as this glass, a generally known glass is used, and although it is not limited to a glass of a specific composition, Pb ₃ O ₄ , Bi ₂ O ₃ , SnO _2. Oxides such as 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. If such occurrence is undesirable, it is preferable not to contain these oxides. Glass components include SiO ₂ , B ₂ O ₃ , ZnO,
CaO, SrO, ZrO2, _etc. are preferred, and the composition ratios of these oxides are: _SiO2 12-33% by weight _{B2O3 20-35} % by weight ZnO or SrO13-33% by weight CaO10-25% by weight _ZRO2 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. 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
CaO _{, B2}
each in place of part or all of O ₃
CaCO ₃ and H ₃ BO ₃ can be used. The same applies to oxides of other components. The alkaline earth metal molybdate and glass powder obtained as described above are mixed, and to this mixed composition, metals in the group such as Au and/or metal oxides thereof, and further the rare earth metals are mixed. Elemental oxides and/or titanium oxide may be added and further mixed to be used as a resistor material, but it is better to heat-treat and pulverize this to make a resistor material. It is preferable in terms of resistance temperature characteristics of the body. The heat treatment temperature is 800℃.
~1200℃ is preferable; if it is outside this range, the resistance value of the finished resistor will be easily affected by slight fluctuations in the composition ratio due to the working conditions of each process 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 nitrogen gas or other inert gas, or a mixed gas containing these gases and hydrogen gas. The composition ratio of each component of the resistor material is as follows: 100 parts by weight of a composition of 30 to 96% by weight of alkaline earth metal molybdate and 4 to 70% by weight of glass powder.
metals and/or their metal oxides in the group of
It is preferable to add 0.05 to 3.00 parts by weight, and when titanium oxide is used in combination, this titanium oxide is added in an amount of 0.01 to 5.00 parts by weight, and when the above rare earth element oxide is used in combination, it is added in an amount of 0.1 to 20.0 parts by weight. Those added are preferred. If the amount of alkaline earth metal molybdate 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 acid salt is too large and the amount of glass is too small, sinterability during firing may deteriorate and it may not be possible to stably hold the material on the circuit board. However, when a resistor is embedded in a laminated circuit board, the molybdate content of the element may not only be greater than the above range, but may also be 100%. Additionally, if the amount of metals and/or metal oxides in the group such as Au mentioned above is too small, the durability in the humidity load test will not improve, and if it is too large, the humidity coefficient will become negative with a large absolute value. Sometimes. Furthermore, if the amount of the rare earth element oxide added is too small, it may not be possible to reduce the rate of change in power operation, and if the amount of titanium oxide is too small, it may be unfavorable in terms of voltage resistance. If there is too much oxide or titanium oxide, the same problem as in the case of metals in the group such as Au and/or their metal oxides occurs. 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 burned. . In this case, it is preferable that the molybdate, which is the main body of the electric resistance, is formed into bulk particles such as spheres, ellipses, and polygons before use. This is because it is preferable that the original matrix remains during the firing process in which the acicular particles grow. A binder such as glass may also be used to form the resistor body material into bulk particles. In order to apply a resistor material made of molybdate and glass, for example, a vehicle is mixed with the resistor material powder to prepare a coating liquid so that silk screen printing can be performed, for example. This vehicle is preferably one that can be burned out in the pre-firing stage.For this purpose, the resin is dissolved or dispersed in an organic vehicle, that is, an organic solvent, and various additives such as plasticizers and dispersants are added as necessary. Preferably added. Examples of the organic solvent include butyl carbitol acetate, butyl carbitol, turpentine oil, etc. 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 substrate, which is further processed as described below to create a resistor. In addition to a 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 the alkaline earth metal 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. Preferably, the resistor material paste is applied to a ceramic green sheet by means such as silk screen printing, and after drying, it is heat treated at 400 to 500°C to decompose and burn the resin component. 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 assembled, 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 shape. After configuring the circuit, it is fired. This firing allows the conductor material and/or resistor material to 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. A circuit wiring board incorporating a conductor and/or a resistor is completed as described above, but cracks, distortions, etc. occur not only between the fired board and the conductor, but also between the fired board and the resistor due to firing. No blistering, 40±2℃, relative humidity 90
Turn on the rated DC voltage for 1.5 hours in ~95% atmosphere,
Even in a humidity load test of 500 hours with a 0.5 hour off cycle, the resistance value change could be >3%. Furthermore, in a high temperature and high humidity atmosphere
Even if it is left for more than 1000 hours, its resistance value is suppressed to change within ±2%, ensuring high reliability. In addition, when combined with titanium oxide,
Even when a high voltage pulse is applied, the resistance value is suppressed to change within ±10%. In addition, when the above rare earth element oxides are used together, the rated voltage can be increased at 70±5℃.
Even when subjected to a power operation test of 1.5 hours on and 0.5 hours off for 240 hours, the rate of change was ±2.
It can be suppressed within %. These are because this resistor matches well with the conductor and fired substrate, and because of the effects of adding metals in the group such as Au and/or their metal oxides, titanium oxide, and oxides of the rare earth elements mentioned above. Although it is possible, the details of the mechanism are not clear. Note that molybdate in the resistor can be observed by X-ray diffraction analysis. Furthermore, lumpy particles and needle-like particles can be observed using a transmission electron microscope. In the present invention, alkaline earth metal molybdates may be used as described above, but instead of these molybdates, some or all of the precursors that become these molybdates 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 mixed material of the oxides that make up glass is alkaline earth metal molybdate.
Metals in the group such as Au and/or metal oxides thereof,
It is sufficient if the precursors of these glass oxides are combined with molybdates of alkaline earth metals and/or their precursors as long as they are fired together with titanium oxide and the oxides of the rare earth elements mentioned above. , a metal in the group such as Au and/or its metal oxide, titanium oxide, and a part or all of this oxide together with the oxide of the rare earth element are made into a paste state as described above, and this is applied to the substrate. In the process of applying the organic matter to the surface, burning it, and then firing it, a glass consisting of the above glass components is formed, and this is combined with alkaline earth metal molybdate and/or its precursor, among the above groups such as Au. metal and/or
Alternatively, any material that can be used to produce a resistor by firing with a metal oxide, titanium oxide, or even an oxide of the rare earth element mentioned above may be used. For example, CaO (calcium oxide), a component of glass material,
Heating CaCO ₃ (calcium carbonate), B ₂ O ₃ (boron oxide) is obtained from heating boric acid (H ₃ BO ₃ ), so CaCO ₃ can be used instead of CaO, some or all of B ₂ O ₃ , respectively. , H ₃ BO ₃ can be used. The resistor material in the present invention is mainly composed of alkaline earth metal molybdate, a metal in the group such as Au and/or its metal oxide, and glass as a result of the treatment process, Furthermore, any material containing these, titanium oxide, and oxides of the above-mentioned rare earth elements as main components may be used. Examples Next, examples of the present invention will be described. 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%. A mixture of glass A was melted at 1400° C. in an alumina crucible, and the melt was poured into water and rapidly cooled. This quenched product was taken out and placed in a pot mill with ethanol, and ground with an alumina ball for 24 hours to obtain a glass powder with a particle size of 10 μm or less. Further, molybdenum oxide and magnesium carbonate were mixed at a molar ratio of 1:1 and heat treated at 700°C for 1 hour to obtain a magnesium molybdate. Next, the glass A powder obtained above, magnesium molybdate, metals in the group such as Au or their metal oxides, titanium oxide, and oxides of the rare earth elements shown in Table 2 were added. The parts were weighed and mixed to give the weight parts shown in each column. Each sample in Table 2 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 to a size of 10 μm. Resistor material powders of glass and magnesium molybdate as described below, metals in the group such as Au or their metal oxides, titanium oxide, and heat-treated powders of oxides of the rare earth elements as described above were obtained. Next, 25 parts by weight of an organic vehicle (90 parts by weight of butyl carbitol, 10 parts by weight of ethyl cellulose) was 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 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
100 parts by weight of ceramic raw material powder consisting of 5.0% by weight, 8 parts by weight of polyvinyl butyral, 8 parts by weight of diethyl phthalate, 0.5 parts by weight of oleic acid, and acetone.
10 parts by weight, 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, and after defoaming treatment, a long ceramic green sheet with a thickness of 200 μm was prepared using the doctor blade method. did. 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. 2, on top of the green sheet piece 1 measuring 9 mm in length and 9 mm in width, 95 parts by weight of copper powder, 5 parts by weight of glass frit, 20 parts by weight of butyl carbitol and 5 parts by weight of ethyl cellulose as an organic vehicle were added. , screen printed a conductor material paste mixed with these using a three-roll mill, and 125
℃ for 10 minutes to form a conductive material coating film 2. Next, the resistor material paste obtained above was screen printed on the green sheet piece 1 in the same manner as above and dried at 125° C. for 10 minutes to form a thick film resistor coating 3. Next, on the green sheet piece 1, the length 6 mm obtained above was
Green sheet pieces 4 each having a width of 9 mm are stacked as shown by the chain lines in the figure and heat-pressed at 100° C. and 150 kg/cm ² . Next, this is heated at 400 to 500℃ in an oxidizing atmosphere such as air.
The green sheet pieces 1, 4, the conductor material coating 2, and the resistor material coating 3 are heated to decompose and burn the residual organic matter. After removing organic matter in this way, _N2
At 950℃ in a mixed gas of 98.5vol% and H ₂ 1.5vol%,
After firing for 1 hour, as shown in FIG. 3, 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. In this multilayer ceramic substrate, no warping or blistering as shown in FIGS. 4 and 5, which will be described later, was observed. The multilayer ceramic substrate of the fired body thus obtained is polished in the layer direction to expose the resistor layer, and the exposed resistor layer is subjected to X-ray diffraction (Cu K α rays).
When analyzed, magnesium molybdate was confirmed. Next, the resistance value (R ₂₅ ) of this thick film resistor 3a at 25°C and the resistance value (R ₁₂₅ ) when heated to 125°C.
was measured using a digital multimeter, and 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
Table 3 shows the results of measuring the resistance value at 25°C after being left for 1000 hours at 95% relative humidity and determining the rate of change. Further, Table 3 shows the results of measuring the rate of change in power operation when the rated power P was set to 1/4 watt (W). This power operation rate of change is determined by calculating the rated voltage E from the following formula, E = √ x ₂₅ (Rated power: P = 1/4 watt (W)), and applying this rated voltage E to the thick film resistor 3a. 70±5℃
With a cycle of 1.5 hours on and 0.5 hours off,
After applying for 245 hours, the resistance value is changed again at 25℃.
R′ ₂₅ was measured, and the rate of change ΔR ₂₅ [%] was determined from the following formula. △R ₂₅ [%] = R' ₂₅ - R ₂₅ / R ₂₅ × 100 In addition, the above rated DC voltage was applied to the thick film resistor 3a in a test chamber at 40±2°C and a relative humidity of 90 to 95%.
Table 3 shows the rate of change in resistance after 500 hours of cycles of 1.5 hours on and 0.5 hours off as durability. Also, with a voltage of 1KV on a 200pF capacitor
After charging for 0.8 seconds, the thick film resistor was discharged for 0.8 seconds, this was repeated three times, and the voltage resistance was determined by calculating the rate of change in resistance after voltage application, and the results are shown in Table 3. Examples 2 to 4 Resistors shown in Table 2 were produced in the same manner as in Example 1, except that calcium molybdate, strontium molybdate, and barium molybdate were used instead of magnesium molybdate, respectively. A multilayer ceramic substrate was prepared using the materials, and thick film resistors formed from the respective resistor materials were measured in the same manner as in Example 1. The results are shown in Tables 4, 5, and 6, respectively. In addition, in each of the above examples, molybdate and glass, titanium oxide or an oxide of the above-mentioned rare earth element added thereto, and furthermore, these titanium oxide and the above-mentioned oxide of the rare earth element added to molybdate and glass. The results of measurements made in the same manner on samples prepared in the same manner except for using each are shown in No. 1 to No. 4, No. 5, No. 6, and No. of each table.
Shown in Nos. 7, 8 and Nos. 9 and 10. Note that the same effect can be obtained even when the metal in the group such as Au and/or its metal oxide is used in combination with a molybdate of another metal. Furthermore, instead of titanium oxide, titanates of alkaline earth metals such as TiB ₂ , TiC, TiN, TiSi ₂ or any mixture containing these and titanium oxide may be used instead of titanium oxide in the above formulation. Pressure resistance is obtained, and in this case, when the above-mentioned rare earth oxides are used in combination, power operation stability is also obtained, and in these cases, the same effect can be obtained by using molybdates of other metals alone or in combination. .

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[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 at 1400°C in vacuum, and the product was mixed with ethanol into alumina balls in a pot mill. The mixture 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 the example 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 4, warpage is observed, and MoSi ₂ ,
Due to the generation of SiO ₂ gas during the decomposition reaction of TaSi ₂ , blistering occurred as shown in FIG. 5, making it impossible to put it to practical use. Note that 11a is the ceramic layer 1a, 14a is the magnetic 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 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 ZnO, ZrO ₂ , CaO, and A ₂ O ₃ were mixed in a ball mill, and the resulting powder was heat-treated at 1200°C in an argon (Ar) gas atmosphere. Grind in a bowl 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 7 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, the rate of change in resistance value is within ±2%, and the durability is within 3%. The material has excellent voltage resistance,
The power operation change rate of the above-mentioned one to which the rare earth element oxide is added is within ±2%, whereas the multilayer ceramic substrate of Comparative Example 1 shows warping, and the multilayer ceramic substrate of Comparative Example 2 has resistance. The rate of change of value is 4
It turns out that it is twice as large. Effects of the Invention According to the present invention, a fired body of a molybdate of an alkaline earth metal and a metal in the group such as Au and/or its metal oxide, titanium oxide, and further the rare earth element For example, molybdates of alkaline earth metals,
Metals in the group such as Au and/or metal oxides thereof,
By using glass, or a resistor material having a composition mainly composed of rare earth element oxides, or even titanium oxide, and firing it together with a ceramic grease sheet in a non-oxidizing atmosphere together with a base metal conductor material, a resistor can be created. By forming a resistor body, the fired body will not warp or bulge during firing, and it will not only reduce the aging of the resistor, especially under high humidity conditions, but also reduce the resistance in humidity load tests. Durability can be improved, and when titanium oxide is used in combination, voltage resistance can also be improved, and furthermore, when the above-mentioned rare earth element oxides are used in combination, the rate of change in power operation can be reduced. In addition, since it is possible to provide an electrical resistor having a fired body in which acicular particles are attached to or close to lump particles,
When an electric resistor is formed by firing a resistor material containing bulk particles of the electric resistor body material together with a ceramic green sheet in a non-oxidizing atmosphere together with, for example, a base metal conductor material, needle-like particles are formed from the surface of the bulk particles. Particles can be grown, excessive reduction can be avoided, and an electrical resistor having an appropriate resistance value can be provided. These satisfy the demands for both miniaturization and cost reduction of a circuit board incorporating a resistor, and contribute to further improvement in the performance of the circuit board. In addition, a molybdate of an alkaline earth metal, a metal in the group such as Au and/or its metal oxide, or these together with titanium oxide, or an oxide of the rare earth element, for example, is heat treated with glass,
When this heat-treated resistor material is fired to form a resistor, the absolute value of the temperature change coefficient of resistance can be reduced, and the performance of the circuit can be further improved.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of the structure of the electrical resistor of the present invention,
Fig. 2 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. 3 is a cross-sectional view of the fired body, FIG. 4 is a cross-sectional view of the fired body when a multilayer structure is formed using conventional resistor material, and FIG. 5 is an explanation showing the state in which gas is generated in the fired body. It is a diagram. In the figure, a is glass, b is lumpy particles, c is acicular particles, 1 and 4 are green sheet pieces, 2 is a conductor material coating, 3 is a resistor material coating, 1a and 14a are porcelain layers, and 2a is a The thick film conductor 3a is a thick film resistor.

Claims (1)

[Claims] 1. Alkaline earth metal molybdate, Au,
An electrical resistor characterized by having a fired body containing at least one metal selected from the group of Ag, Pt, Ru, Ni, Cu, Co, and Pd and/or a metal oxide thereof. 2 The fired body contains at least one kind of alkaline earth metal molybdate and its precursor, Au, Ag,
Claims characterized in that the resistor material is fired from a resistor material containing as a main component at least one metal selected from the group of Pt, Ru, Ni, Cu, Co, and Pd and/or its metal oxide. The electrical resistor according to range 1. 3 The main component of the resistor material is at least one of an alkaline earth metal molybdate and its precursor.
A composition comprising 30 to 96% by weight of seeds in terms of molybdate of the alkaline earth metal and 4 to 70% by weight of glass, based on 100 parts by weight of the composition.
0.05-3.00 parts by weight of Au, Ag, Pt, Ru, Ni, Cu,
The electrical resistor according to claim 2, characterized in that it contains at least one metal selected from the group of Co and Pd and/or its metal oxide. 4 It has a lumpy particle, an acicular particle attached to the lumpy particle or exists in the vicinity of the lumpy particle, and a glass layer, and is selected from the group of Au, Ag, Pt, Ru, Ni, Cu, Co, and Pd. A fired body containing at least one metal and/or its metal oxide, wherein the lump particles contain a molybdate of an alkaline earth metal, and the acicular particles are a reduction product of the molybdate. An electrical resistor characterized by containing. 5. The electrical resistor according to claim 4, wherein the acicular particles are reduction products produced by reducing the surface of the lumpy particles. 6 Alkaline earth metal molybdate and Au,
An electrical resistor characterized by having a fired body containing at least one metal selected from the group of Ag, Pt, Ru, Ni, Cu, Co, and Pd and/or its metal oxide and titanium oxide. . 7 The fired body contains at least one kind of alkaline earth metal molbdate and its precursor, Au, Ag,
It is characterized by being fired from a resistor material containing at least one metal selected from the group of Pt, Ru, Ni, Cu, Co, and Pd and/or its metal oxide and titanium oxide as main components. An electrical resistor according to claim 6. 8 Alkaline earth metal molybdate and Au,
At least one metal and/or its metal oxide selected from the group of Ag, Pt, Ru, Ni, Cu, Co, Pd, Y, La, Ce, Pr, Nd, Sm, Eu, Gd,
An electrical resistor characterized by having a fired body containing an oxide of at least one element selected from the group of Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, and Pm. 9 The fired body contains at least one molybdate of an alkaline earth metal and its precursor, Au, Ag,
At least one metal selected from the group of Pt, Ru, Ni, Cu, Co, Pd and/or its metal oxide, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb,
The patent claim is characterized in that the resistor material is fired from a resistor material containing as a main component an oxide of at least one element selected from the group of Dy, Ho, Er, Tm, Yb, Lu, Sc, and Pm. The electrical resistor according to range 8. 10 alkaline earth metal molybdate;
At least one metal selected from the group of Au, Ag, Pt, Ru, Ni, Cu, Co, Pd and/or its metal oxide, titanium oxide, Y, La, Ce,
Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er,
An electrical resistor characterized by having a fired body containing an oxide of at least one element selected from the group of Tm, Yb, Lu, Sc, and Pm. 11 The fired body contains at least one of an alkaline earth metal molybdate and its precursor, Au,
At least one metal selected from the group of Ag, Pt, Ru, Ni, Cu, Co, Pd and/or its metal oxide, titanium oxide, Y, La, Ce, Pr, Nd,
Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,
11. The electrical resistor according to claim 10, which is fired from a resistor material containing as a main component an oxide of at least one element selected from the group of Lu, Sc, and Pm. 12 The main components are at least one of alkaline earth metal molybdates and their precursors, Au,
A resistor material obtained by heat treating a resistor material containing at least one metal selected from the group of Ag, Pt, Ru, Ni, Cu, Co, and Pd and/or its metal oxide Calcined using materials, alkaline earth metal molybdate and Au, Ag, Pt,
A method for producing an electrical resistor, comprising obtaining an electrical resistor comprising a fired body containing at least one metal selected from the group of Ru, Ni, Cu, Co, and Pd and/or its metal oxide. . 13 The main components of the resistor material before heat treatment are 30 to 96% by weight of at least one of an alkaline earth metal molybdate and its precursor, calculated as the alkaline earth metal molybdate, and glass. 4~
and 0.05 to 3.00 parts by weight of Au, Ag, Pt, based on 100 parts by weight of the composition.
The method for producing an electrical resistor according to claim 12, characterized in that the electrical resistor is made of at least one metal selected from the group of Ru, Ni, Cu, Co, and Pd and/or its metal oxide. .