JP2005209627A - Conductive material, resistive paste using this, resistor, and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resistor of high resistance attaining both temperature characteristics (TCR, temperature coefficient of resistance) and voltage-withstanding characteristics (STOL, short-time overload) as well as a conductive material with restrained variation with time. <P>SOLUTION: The conductive material contains Ru complex oxide with its basic composition expressed in ARuO<SB>3</SB>(wherein, A denotes any given element), and with a part of Ru substituted with at least a kind out of Ti and Zr. The given element A is at least a kind selected from Ca, St, and Ba. When expressed in ARu<SB>(1-x)</SB>S<SB>x</SB>O<SB>3</SB>(provided, S denotes at least a kind out of Ti and Zr, and x denotes a substitution ratio), the substitution ratio is 0.01 to 0.50. The Ru complex oxide has a perovskite type crystalline structure, with a part of an Ru site substituted with at least a kind out of Ti and Zr. The Ru complex oxide is mixed with a glass composition and an organic vehicle to make up the resistive paste. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel oxide-based conductive material, and further relates to a resistor paste, a resistor, and an electronic component formed using the conductive material.

For example, a resistor paste is generally composed of a glass material, a conductive material, and an organic vehicle for adjusting the resistance value and imparting bonding properties. The resistor paste is printed on a substrate and then fired. As a result, a thick film resistor having a thickness of about 5 to 20 μm is formed. In this type of resistor paste (thick film resistor), usually, ruthenium oxide (RuO ₂ ), lead ruthenium oxide or the like is used as the conductive material, and lead oxide (PbO) glass or the like is used as the glass. It is used.

  In recent years, environmental issues have been actively discussed, and elimination of harmful substances such as lead from electronic components is being promoted. The resistor paste and the thick film resistor are no exception, and research is being conducted to make them lead-free.

  As one of the problems in making the resistor paste lead-free, there is a compatibility between temperature characteristics (TCR) and withstand voltage characteristics (STOL) particularly in a resistor paste having a high resistance (10 kΩ / □ or more). For example, when adjusting the TCR by adding a metal oxide, which has been used in conventional lead-based resistor pastes, to a lead-free composition as it is, changes in resistance due to voltage application are compared with the lead-based composition. As a result, it is difficult to achieve both TCR and STOL.

Under these circumstances, a glass paste containing no lead, a conductive material containing no lead, and a resistor paste mainly composed of an organic vehicle, CaTiO ₃ or NiO is added as an additive, and temperature characteristics (TCR) And the withstand voltage characteristic (STOL) have been attempted (see, for example, Patent Document 1).

In Patent Document 1, it is preferable that the resistor paste contains, for example, CaTiO ₃ more than 0 vol%, 13 vol% or less, or NiO more than 0 vol%, 12 vol% or less, and further additives such as CuO, ZnO, MgO, etc. There is a description that it is preferable to add them at the same time, and as a result, lead suitable for obtaining a resistor having a low temperature characteristic (TCR) and a low withstand voltage characteristic (STOL) while having a high resistance value. It is said that it is possible to provide a free resistor paste.
JP 2003-197405 A

  However, as in the invention described in Patent Document 1, in a resistor formed using a resistor paste whose characteristics are adjusted by containing a large amount of additives, a reliability test, for example, a aging test (85 ° C., At 85% RH, a change in resistance value after 1000 hours), the reliability tends to be lower than that of a conventional resistor paste having a lead-based composition, which is a major problem. The reason for the decrease in reliability is that the resistor paste contains a large amount of additive, and the binding of the conductive material and additive by glass becomes insufficient.

On the other hand, composite oxides such as SrRuO ₃ , BaRuO ₃ , and CaRuO ₃ are also known as conductive materials that do not contain lead and can increase resistance. However, when these composite oxides are used as a conductive material, it is still difficult to obtain a resistor having both characteristics such as temperature characteristics (TCR) and withstand voltage characteristics (STOL).

  The present invention has been proposed in order to solve such problems of the prior art. That is, the present invention has a high resistance value of 10 kΩ / □ or more, can achieve both temperature characteristics (TCR) and withstand voltage characteristics (STOL) without requiring a large amount of additives, and is reliable. An object of the present invention is to provide a conductive material capable of realizing a high-resistance resistor. Furthermore, the present invention provides a resistor paste, a resistor, and an electronic component that have high resistance, excellent temperature characteristics (TCR) and withstand voltage characteristics (STOL), and little change with time by using the conductive material. For the purpose.

  The inventors of the present invention do not need a large amount of additives to sufficiently bind the conductive material, suppress the change with time, and increase the reliability, and have a temperature characteristic (TCR) and a withstand voltage characteristic (STOL). We thought that it would be effective to use a conductive material that can be compatible, and have been researching it for a long time. As a result, it has been concluded that a Ru composite oxide in which a part of the Ru site is substituted with Ti or Zr is a conductive material suitable for such a purpose.

The present invention has been completed based on such findings. That is, the conductive material of the present invention has a basic composition represented by ARuO ₃ (wherein A represents an arbitrary element), and Ru is partially substituted with at least one of Ti or Zr. It contains a composite oxide.

The resistor paste of the present invention is a resistor paste containing a glass composition and a conductive material, which are mixed with an organic vehicle, and the basic composition of the resistor paste is ARuO ₃ (however, In the formula, A represents an arbitrary element.), And a Ru composite oxide in which a part of Ru is substituted with at least one of Ti or Zr. Furthermore, the resistor of the present invention is characterized by being formed using the resistor paste, and the electronic component of the present invention includes the resistor formed in this way, or the It is characterized by using a conductive material.

A Ru composite oxide in which the basic composition is represented by ARuO ₃ (wherein A represents an arbitrary element), and a part of Ru is substituted with at least one of Ti or Zr, is obtained by the present inventors. It is a newly developed conductive material. The Ru composite oxide of the present invention has better TCR characteristics and STOL characteristics as compared with unsubstituted conventional Ru composite oxides. Therefore, such Ru composite oxides can be used as resistor pastes and resistor conductive materials. When used as a conductive material, TCR characteristics and STOL characteristics are compatible with high resistance of 10 kΩ / □ or more. Further, when the Ru composite oxide is used as a conductive material, a large amount of additive is not required, so that a change with time is suppressed and reliability is ensured.

  When the conductive material of the present invention is applied to, for example, a resistor paste or a resistor, it has a high resistance and can achieve both TCR characteristics and STOL characteristics, and does not require a large amount of additives, so it changes with time. Thus, a highly reliable resistor can be obtained. Therefore, according to the present invention, it is possible to provide a resistor paste, a resistor, and an electronic component that have high resistance, excellent temperature characteristics (TCR) and withstand voltage characteristics (STOL), and little change with time.

  Hereinafter, a conductive material, a resistor paste, a resistor, and an electronic component to which the present invention is applied will be described in detail.

The conductive material of the present invention has a basic composition represented by ARuO ₃ (wherein A represents an optional element), and Ru is partly substituted with at least one of Ti or Zr. It contains things. In the Ru composite oxide, for example, when the optional element A is at least one of Ca, Sr, and Ba, it has a resistivity equivalent to that of Pb ₂ Ru ₂ O ₆ or the like conventionally used for high resistance applications. A conductive material can be obtained.

A specific composition of the Ru composite oxide is represented by ARu _(1-x) S _x O ₃ (wherein S represents at least one of Ti or Zr, and x represents a substitution ratio). Can be mentioned. In this case, the substitution ratio x is preferably 0.01 to 0.50. When the substitution ratio x is less than 0.01, the effect is small and the change with time cannot be made sufficiently small. On the other hand, if the substitution ratio x is too large, a phenomenon such as the fact that the entire amount is not substituted at the Ru site occurs, and the effect of suppressing change with time may be reduced. More preferably, the substitution ratio is 0.03 to 0.30.

The Ru composite oxide usually has a perovskite crystal structure (ABO ₃ ) and has a structure in which a part of the Ru site is substituted by Ti or Zr. Of course, the present invention is not limited to this, and any material having the above composition may be used. In particular, when the Ru site is partly substituted with Ti or Zr in the perovskite crystal structure, the material is excellent as a conductive material. Express characteristics. A Ru composite oxide composed of a single phase of a perovskite crystal structure is suitable from the viewpoints of achieving both TCR and STOL and suppressing aging. Whether or not the Ru composite oxide has a perovskite crystal structure can be easily determined by comparing an X-ray diffraction chart with an ASTM card. Further, the fact that part of the Ru site is substituted with Ti or Zr can also be determined by the presence or absence of a peak derived from the subphase in X-ray diffraction.

  On the other hand, the resistor paste of the present invention contains a glass composition, a conductive material, and, if necessary, an additive, and these are mixed with an organic vehicle. The aforementioned Ru composite oxide is used as the conductive material. The content of the conductive material in the resistor paste is 7.6% by mass to 51.0% by mass when the total mass of the glass composition, the conductive material, and the additive is 100% by mass. Is preferred. More preferably, it is 10 mass%-45 mass%. If the content of the conductive material is too low below the above range, the resistance value becomes too high, which may make it unsuitable for use as a resistor paste. On the other hand, if the content of the conductive material exceeds the above range, the binding of the conductive material by the glass composition becomes insufficient, and the reliability may be lowered.

  The glass composition is not particularly limited, but in the present invention, it is preferable to use a lead-free glass composition that substantially does not contain lead for environmental protection. In the present invention, “substantially free of lead” means not containing lead exceeding the amount that cannot be said to be an impurity level, and the amount of impurity level (for example, the content in the glass composition). Is about 0.05% by mass or less). Lead may be contained in a trace amount as an inevitable impurity.

As a raw material for the glass composition, a network-forming oxide component and a modified oxide component are usually mixed and used. Examples of the network-forming oxide component include B ₂ O ₃ and SiO ₂ . Further, as the main modifying oxide component, at least one selected from alkaline earth oxides, specifically, CaO, SrO, and BaO is used. Moreover, it is preferable that at least one of ZrO ₂ , Al ₂ O ₃ , and ZnO is contained as the other modified oxide component in addition to the main modified oxide component.

Hereinafter, to describe the content in the glass composition of each component, B ₂ O ₃ as a network-forming oxide component preferably contains 15 to 50 mol% in the glass composition. More preferably, it is 20-45 mol%. When the content of B ₂ O ₃ is low, the softening point of the glass composition is high, so when a resistor is formed at a predetermined firing temperature, the resistor is not sufficiently sintered and the reliability is significantly reduced. There is a risk of causing. On the other hand, when the content of B ₂ O ₃ is too large, the water resistance of the glass composition is lowered, so that the reliability of the resistor may be significantly lowered.

Similarly, SiO ₂ as a network-forming oxide component is preferably contained in an amount of 20 to 55 mol% in the glass composition. More preferably, it is 25-50 mol%. When the content of SiO ₂ is small, the water resistance of the glass composition is lowered, so that there is a fear that the reliability when a resistor is used is remarkably lowered. On the contrary, when the content of SiO ₂ is too high, the softening point of the glass composition becomes high. Therefore, when a resistor is formed at a predetermined firing temperature, sintering of the resistor becomes insufficient and reliability is increased. There is a risk of significant reduction.

  At least one selected from CaO, SrO, and BaO as the main modifying oxide component is preferably contained in an amount of 25 to 45 mol% in the glass composition. More preferably, it is 27-40 mol%. If the content of the main modifying oxide component is too small below the above range, the reactivity with the conductive material may be reduced, and the TCR and STOL characteristics may be deteriorated. On the other hand, when the content of the main modifying oxide component exceeds the above range, excessive metal oxide deposition may occur when the resistor is formed, which may deteriorate the characteristics and reliability.

At least one of ZrO ₂ , Al ₂ O ₃ , and ZnO as other modified oxide components is preferably contained in the glass composition in an amount of 2 to 10 mol%. More preferably, it is 3-7 mol%. When the content of the other modified oxide component is too small below the above range, the water resistance of the glass composition is lowered, so that the reliability when the resistor is used may be significantly lowered. On the other hand, when the content of other modified oxide components exceeds the above range, excessive deposition of metal oxides may occur when the resistor is formed, which may deteriorate characteristics and reliability.

Moreover, although arbitrary oxides may be contained as a 3rd modification oxide component, it is preferable that content in the glass composition shall be about 5 mol% or less. If the content of the third modified oxide component exceeds the above range, the content may be deteriorated depending on the type of the added oxide. Examples of the third modified oxide component include MgO, TiO ₂ , SnO ₂ , K ₂ O, Na ₂ O, Li ₂ O, CuO, MnO, Fe ₂ O ₃ , Cr ₂ O ₃ , and Y _2. Examples thereof include O ₃ and V ₂ O ₅ .

  The content of the glass composition in the resistor paste is 47.3 mass% to 90.2 mass% when the total mass of the glass composition, the conductive material, and the additive is 100 mass%. Is preferred. More preferably, it is 52 mass%-90 mass%. When the content of the glass composition is less than 47.3 mass%, the binding of the conductive material and the additive becomes insufficient, and the reliability may be significantly lowered. On the other hand, if the content of the glass composition exceeds the above range, the resistance value becomes too high, and there is a possibility that it is not suitable for use as a resistor paste.

  In addition to the conductive material and glass composition described above, the resistor paste may contain an additive for the purpose of adjusting characteristics. The content of the additive in the resistor paste is preferably 1.0% by mass to 16.8% by mass when the total mass of the glass composition, the conductive material, and the additive is 100% by mass. . More preferably, it is 1.6 mass%-8.6 mass%. If the content of the additive is less than the above range, it is difficult to adjust the characteristics sufficiently. On the other hand, when the content of the additive is too large, the binding of the conductive material and the additive becomes insufficient, and the reliability may be significantly reduced.

Any metal oxide can be used as the additive. _{Specifically, CuO, MgO, TiO 2,} SnO 2, CoO, MnO, Fe 2 O 3, Cr 2 O 3, Y 2 O 3, V 2 O 5, NiO, SrTiO 3, BaTiO 3, CaTiO 3 or the like Is exemplified. Among these, CuO is an oxide that is highly effective as a TCR regulator. When CuO is used as an additive, the content of CuO in the resistor paste is 1.0% by mass to 8.% when the total mass of the glass composition, the conductive material, and the additive is 100% by mass. The content is preferably 1% by mass. More preferably, it is 1.6 mass%-6.2 mass%. When the content of CuO is small, the TCR adjustment effect becomes insufficient and the TCR characteristics of the resistor may be deteriorated. On the other hand, when the content of CuO is too large, the STOL characteristics may be deteriorated.

  The organic vehicle has a role of kneading the conductive material, the glass composition and the additive into a paste, and any of those used for this type of resistor paste can be used. An organic vehicle is prepared by dissolving a binder in an organic solvent. It does not specifically limit as a binder, For example, what is necessary is just to select suitably from various binders, such as an ethyl cellulose and polyvinyl butyral. The organic solvent is not limited, and may be appropriately selected from various organic solvents such as terpione, butyl carbitol, acetone, and toluene. Furthermore, in order to adjust the physical properties of the resistor paste, various additives such as a dispersant may be added.

  The organic vehicle compounding ratio is a ratio (W2 / W1) of the total mass (W1) of the glass composition, the conductive material, and the additive to the mass of the organic vehicle (W2) (W2 / W1). -4 (W2: W1 = 1: 0.25 to 1: 4) is preferable. More preferably, the ratio (W2 / W1) is 0.5-2. If the ratio is outside the above range, a resistor paste having a viscosity suitable for forming a resistor on, for example, a substrate may not be obtained.

In order to form the resistor, the resistor paste containing the above-described components may be printed (applied) on the substrate by a method such as screen printing and fired at a temperature of about 850 ° C. As the substrate, a dielectric substrate such as an Al ₂ O ₃ substrate or a BaTiO ₃ substrate, a low-temperature fired ceramic substrate, an AlN substrate, or the like can be used. The substrate form may be any of a single layer substrate, a composite substrate, and a multilayer substrate. In the case of a multilayer substrate, the resistor may be formed on the surface or inside.

  In forming the resistor, a conductive pattern to be an electrode is usually formed on the substrate. This conductive pattern can be formed by printing a conductive paste containing a good conductive material such as Ag or Pt, for example. . Further, a protective film such as a glass film may be formed on the surface of the formed resistor.

  The resistor can be applied to electrode portions such as a capacitor and an inductor as well as a single-layer or multilayer circuit board and a chip resistor. Further, the conductive material of the present invention is not limited to the resistor paste or the conductive material of the resistor, but can be used as a conductive material for any application. For example, the conductive material of the present invention is directly included on a substrate. It is also possible to form a pattern and use it as an electrode or wiring.

  Hereinafter, specific examples of the present invention will be described based on experimental results.

(Production of conductive material)
In the Ru-based composite oxide ARu _(1-x) S _x O ₃ (wherein S represents at least one of Ti or Zr, and x represents a substitution ratio), the optional element A includes Ca, Sr, Ba, substitution element S, Ti, Zr, substitution ratio x = 0 to 0.5, CaCO ₃ , SrCO ₃ , BaCO ₃ powder and RuO ₂ powder, TiO ₂ or ZrO ₂ Then, they were mixed with a ball mill and dried.

The obtained powder was heated to 1200 ° C. at a rate of 5 ° C./minute, held at that temperature for 5 hours and fired, and then cooled to room temperature at a rate of 5 ° C./minute, whereby the Ru-based composite oxide A powder was obtained. The obtained powder was pulverized with a ball mill. Further, each Ru-based composite oxide powder was subjected to X-ray diffraction to confirm whether or not a single phase having a perovskite crystal structure was obtained. The obtained conductive material (Ru-based composite oxide) is shown in Table 1. Moreover, about the sample 4, the X-ray-diffraction chart before and behind baking is shown in FIG.1 and FIG.2. FIG. 1 is an X-ray diffraction chart before firing, and FIG. 2 is an X-ray diffraction chart after firing. As shown in FIG. 1, peaks of CaCO ₃ , RuO ₂ and TiO ₂ are mixed before firing, but only peaks of CaRuO ₃ are seen after firing, as shown in FIG. The peak of was hardly seen. Therefore, this sample 4 is a single phase of a perovskite crystal structure, and it is presumed that a part of the Ru site is substituted by Ti. On the other hand, it was confirmed that Sample 6 having a high Ti substitution ratio of 0.50 is a mixed phase of CaRuO ₃ and CaTiO ₃ .

(Preparation of glass composition)
A predetermined amount of oxides such as B ₂ O ₃ , SiO ₂ , CaCO ₃ , SrCO ₃ , BaCO ₃ , ZrO ₂ , Al ₂ O ₃ were weighed, mixed in a ball mill, and then dried. The obtained powder was heated to 1300 ° C. at a rate of 5 ° C./minute, held at that temperature for 1 hour, and then rapidly cooled by being poured into water to be vitrified. The obtained vitrified product was pulverized with a ball mill to obtain a glass composition powder. The composition of the produced glass composition is shown in Table 2.

(Production of organic vehicle)
Using ethyl cellulose as the binder and terpineol as the organic solvent, the binder was dissolved while heating and stirring the organic solvent to prepare an organic vehicle.

(Preparation of resistor paste)
The conductive material powder prepared as described above, the glass composition powder, the additive, and the organic vehicle were weighed so as to have each composition, and kneaded with a three-roll mill to obtain a resistor paste. The ratio of the total mass of the conductive material powder, the glass composition powder, and the additive powder to the mass of the organic vehicle is 1: 1 by mass so that the obtained resistor paste has a viscosity suitable for screen printing. A resistor paste was prepared by blending in the range of 0.25 to 1: 4.

(Production of resistor)
On a 96% alumina substrate, the Ag—Pt conductor paste was screen printed in a predetermined shape and dried. The Ag ratio in the Ag-Pt conductor paste was 95% by mass, and the Pt ratio was 5% by mass. This alumina substrate was placed in a belt furnace and baked in a pattern of 1 hour from charging to discharging. The baking temperature at this time was 850 ° C., and the holding time at that temperature was 10 minutes.

  On the alumina substrate on which the conductor was formed in this manner, the resistor paste prepared previously was applied in a pattern of a predetermined shape (1 mm × 1 mm square shape) by screen printing and dried. Thereafter, the resistor paste was baked under the same conditions as the conductor baking to obtain a thick film resistor.

(Characteristic evaluation of resistors)
(1) Resistance value
Measured with Agilent Technologies product number 34401A. The average value of 24 samples was determined.
(2) TCR
Based on the room temperature of 25 ° C., the rate of change in resistance value when the temperature was changed to 125 ° C. was determined. The average value of 10 samples. If the resistance values at 25 ° C and 125 ° C are R25 and R125 (Ω / □), TCR (ppm / ° C) = (R25-R125) / R25 / 100 × 1000000, and TCR <± 100 ppm / ° C It becomes the standard.
(3) STOL (withstand voltage characteristics)
A test voltage was applied to the thick film resistor for 5 seconds, and the change rate of the resistance value before and after that was determined. The average value of 10 samples. Test voltage = 2.5 × rated voltage, rated voltage = √ (R / 8), and R is a resistance value (Ω / □). For resistors having a resistance value with the calculated test voltage exceeding 200V, the test voltage was 200V. STOL <± 5.0% is a standard for characteristics.
(4) Time-dependent change The change rate of the resistance value when it was left for 1000 hours at 85 degreeC and 85% RH was measured. Change with time ≦ ± 1.0% is a criterion for characteristics.

(Examination on composition of conductive material (Ru composite oxide))
Samples 1 to 14 with different conductive materials were prepared, and the characteristics of the resistor (resistance value, TCR, STOL, change with time) were evaluated. The results are shown in Table 3. The same applies to the following tables, but a sample outside the range defined in the present invention (corresponding to a comparative example) is marked with *.

  As is apparent from Table 3, Samples 3 to 14 in which Ru composite oxides in which a part of Ru sites are substituted with Ti and Zr are used as the conductive material have both TCR and STOL characteristics, and patent documents. Compared with the sample 1 corresponding to the conventional example disclosed in No. 1 and the sample 2 using the Ru composite oxide not substituted with Ti or Zr, the change with time is also significantly smaller. In particular, in Samples 4 to 6 and Samples 8 to 14 using Ru composite oxides in which the substitution ratio x of Ti and Zr is 0.03 to 0.30, a change with time of 1.0% or less is realized.

(Study on the ratio of conductive material to glass composition)
Samples 15 to 20 were prepared by changing the blending ratio of the conductive material and the glass composition, and the characteristics of the resistor were evaluated. The results are shown in Table 4.

  Naturally, as shown in Table 4, the resistance value increases as the ratio of the conductive material decreases, and the resistance value decreases as the ratio of the conductive material increases. In Samples 16 to 19 in which the ratio of the conductive material was 7.6 to 51.0% by mass, good resistance values of 10 kΩ / □ and TCR and STOL characteristics were obtained. 0% or less is realized.

(Study on additives)
Samples 21 to 32 were prepared by changing the type and amount of the additive, and the characteristics of the resistor were evaluated. The results are shown in Table 5.

  In Samples 21 to 25 using CuO as an additive, degradation of TCR characteristics is conspicuous in Sample 21 in which the addition amount of CuO is small and Sample 25 in which the addition amount of CuO is excessive. In Samples 26 to 32, in which additives were added in combination, the change with time exceeded 1.0% in Sample 29 in which the amount of additive added exceeded 18% by mass.

(Examination on types of glass composition)
Samples 33 to 51 were prepared by changing the type of the glass composition, and the characteristics of the resistor were evaluated. The results are shown in Table 6. As is clear from Table 6, good characteristics are obtained by setting the composition of the glass composition within the range described above.

It is an X-ray diffraction chart before baking of a conductive material (sample 4). It is an X-ray diffraction chart after baking of a conductive material (sample 4).

Claims (24)

The basic composition is represented by ARuO ₃ (wherein A represents an arbitrary element), and contains a Ru composite oxide in which a part of Ru is substituted with at least one of Ti or Zr. Conductive material.   2. The conductive material according to claim 1, wherein the arbitrary element A is at least one selected from Ca, Sr, and Ba. The Ru composite oxide is represented by ARu _(1-x) S _x O ₃ (wherein S represents at least one of Ti or Zr, and x represents a substitution ratio), and the substitution ratio x is 0. The conductive material according to claim 1, wherein the conductive material is 0.01 to 0.50.   The conductive material according to claim 3, wherein the substitution ratio is 0.03 to 0.30.   The conductive material according to claim 1, wherein the Ru composite oxide has a perovskite crystal structure.   6. The conductive material according to claim 5, wherein in the perovskite crystal structure, a part of Ru site is substituted with at least one of Ti or Zr. A resistor paste containing a glass composition and a conductive material, which is mixed with an organic vehicle,
As the conductive material, a Ru composite oxide in which the basic composition is represented by ARuO ₃ (wherein A represents an arbitrary element), and a part of Ru is substituted with at least one of Ti or Zr. A resistor paste characterized by containing.   8. The resistor paste according to claim 7, wherein the arbitrary element A constituting the Ru composite oxide is at least one selected from Ca, Sr, and Ba. The Ru composite oxide is represented by ARu _(1-x) S _x O ₃ (wherein S represents at least one of Ti or Zr, and x represents a substitution ratio), and the substitution ratio x is 0. The resistor paste according to claim 7 or 8, wherein the resistor paste is 0.01 to 0.50.   The resistor paste according to claim 9, wherein the substitution ratio is 0.03 to 0.30.   11. The resistor paste according to claim 7, wherein the Ru composite oxide has a perovskite crystal structure.   The resistor paste according to claim 11, wherein in the perovskite crystal structure, a part of Ru site is substituted with at least one of Ti or Zr.   The resistor paste according to claim 7, further comprising an additive.   When the total mass of the glass composition, conductive material, and additives is 100, the ratio of the conductive material is 7.6% to 51.0%, and the ratio of the glass composition is 47. The resistor paste according to claim 13, wherein the resistor paste is 3% to 90.2%, and the ratio of the additive is 1.0% to 16.8%. Said glass composition comprises B ₂ O ₃ and SiO ₂ is contained as a network-forming oxide component, CaO as main modifying oxide component, SrO, according to claim 7, characterized in that it comprises at least one of BaO Resistor paste. In the glass composition, the content of B ₂ O ₃ as a network-forming oxide component is 15 mol% to 50 mol%, the content of SiO ₂ is 20 mol% to 55 mol%, the main modifier oxide ingredient The resistor paste according to claim 15, wherein the content of the resistor is 25 mol% to 45 mol%.   The resistor paste according to claim 16, further comprising other modified oxide components in addition to the main modified oxide component. The resistor paste according to claim 17, wherein the other modified oxide component includes at least one of Al ₂ O ₃ , ZrO ₂ , and ZnO.   The resistor paste according to claim 17 or 18, wherein a content of the other modified oxide component is 2 mol% to 10 mol%.   15. The resistor paste according to claim 13, wherein CuO is included as the additive.   8. The resistor according to claim 7, wherein the ratio of the total mass of the glass composition, the conductive material, and the additive to the mass of the organic vehicle is 1: 0.25 to 1: 4. paste.   A resistor formed using the resistor paste according to any one of claims 7 to 21.   An electronic component comprising the resistor according to claim 22.   An electronic component using the conductive material according to any one of claims 1 to 6 as a conductive material.

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