JP2005209737A - Conductive material and its production process, resistor paste, resistor, electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive material having a resistance as high as 10 kΩ/square or above in which both temperature characteristics (TCR) and withstand voltage characteristics (STOL) can be satisfied. <P>SOLUTION: The conductive material contains an Ru based composite oxide having basic composition represented by A<SB>(x)</SB>RuO<SB>3</SB>(A is an arbitrary element), where 0<x<1. The Ru based composite oxide is produced by calcinating a mixture mixing specified quantities of a compound containing an arbitrary element A and RuO<SB>2</SB>. When the Ru based composite oxide having basic composition represented by A<SB>(x)</SB>RuO<SB>3</SB>, where 0<x<1, is produced, a compound containing an arbitrary element A and RuO<SB>2</SB>are mixed at such a ratio as a relation 0<X<Y=1 is satisfied in the mixture, assuming the quantity of the arbitrary element A is X mol and the quantity of RuO<SB>2</SB>is Y mol. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a conductive material containing a novel Ru-based composite oxide, a method for producing the same, a resistor paste, a resistor, and an electronic component.

For example, a resistor paste is generally composed of a glass composition for adjusting a resistance value and imparting bonding properties, a conductive material, and an organic vehicle as main components, and after printing this on a substrate, By baking, 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 such circumstances, in a resistor paste mainly composed of a lead-free glass composition, a lead-free conductive material, and an organic vehicle, CaTiO ₃ or NiO is added as an additive, and temperature characteristics (TCR ) And withstand voltage characteristics (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 TCR characteristics are adjusted by adding a large amount of additives, a resistor paste having a conventional lead-based composition is used. The STOL characteristic tends to be lower than that in the case of the above. Therefore, it is necessary to further improve STOL characteristics in a state where no additive is added, that is, in the stage of a resistor formed using a resistor paste having a composition composed of a glass composition and a conductive material.

  Therefore, the present invention has been proposed in view of such a conventional situation, and has a high resistance value of, for example, 10 kΩ / □ or more, and achieves both temperature characteristics (TCR) and withstand voltage characteristics (STOL). It is an object of the present invention to provide a conductive material capable of realizing a resistor that can be used and a manufacturing method thereof. The present invention also provides a resistor paste having high resistance, excellent temperature characteristics (TCR) and withstand voltage characteristics (STOL), and excellent thermal stability by using the conductive material, and the resistor. It is an object of the present invention to provide a resistor manufactured using a paste, and an electronic component having the resistor.

The inventors of the present invention conducted long-term research on a conductive material capable of achieving both temperature characteristics (TCR) and withstand voltage characteristics (STOL). As a result, Ru has a basic composition represented by A _(x) RuO _3. As a result, it was concluded that a Ru-rich Ru-based composite oxide in which x is less than 1 in the formula is a conductive material suitable for such a purpose.

The present invention has been completed based on such findings. That is, the conductive material according to the present invention is a Ru-based composite oxide in which the basic composition is represented by A _(x) RuO ₃ (wherein A is an arbitrary element), and 0 <x <1. It is characterized by containing. The resistor paste according to the present invention includes a glass composition and a conductive material, which are mixed with an organic vehicle, and the conductive material has a basic composition of A _{(x )} RuO ₃ (wherein A is an optional element), and is characterized in that it contains a Ru-based composite oxide where 0 <x <1. Furthermore, the resistor according to the present invention is formed using the resistor paste. Furthermore, an electronic component according to the present invention includes the resistor.

A Ru-based composite oxide in which the basic composition used as the conductive material is represented by A _(x) RuO ₃ (wherein A is an arbitrary element) and 0 <x <1 is x = 1. Compared to a conventional Ru-based composite oxide (ARuO ₃ ), the material is superior in both TCR characteristics and STOL characteristics. Therefore, the Ru-based composite oxide is used as a resistor paste and a conductive material for a resistor. By using it, both TCR characteristics and STOL characteristics can be achieved at a high resistance of 10 kΩ / □ or more.

In addition, the method for producing a conductive material according to the present invention includes firing a mixture obtained by mixing a predetermined amount of a compound containing an arbitrary element A and RuO ₂ , wherein the basic composition is represented by A _(x) RuO ₃ , , 0 <x <1, when the amount of the arbitrary element A is X mol and the amount of RuO2 is Y mol, 0 <X <Y = 1 in the mixture. The compound containing the optional element A and the RuO ₂ are mixed so that the ratio is as follows.

In the method for producing a conductive material of the present invention, the ratio of the arbitrary elements A and Ru is adjusted to the ratio of the arbitrary elements A and Ru in the obtained Ru-based composite oxide at the stage of the mixture before firing. Then, by firing, the basic composition is represented by A _(x) RuO ₃ (where 0 <x <1), and when used as a resistor, the TCR has a high resistance of 10 kΩ / □ or more. It is possible to obtain a Ru-based composite oxide capable of satisfying both characteristics and STOL characteristics.

  When the conductive material of the present invention is applied to, for example, a resistor paste or a resistor, it is possible to obtain a resistor that has high resistance and can achieve both TCR characteristics and STOL characteristics. Therefore, according to the present invention, it is possible to provide a resistor paste, a resistor, and an electronic component that have high resistance and excellent temperature characteristics (TCR) and withstand voltage characteristics (STOL).

  Further, according to the method for producing a conductive material of the present invention, when used in a resistor paste or a resistor, a Ru-based composite oxide capable of achieving both high resistance and TCR characteristics and STOL characteristics is obtained. be able to.

  Hereinafter, a conductive material according to the present invention, a manufacturing method thereof, a resistor paste containing the conductive material, a resistor formed using the resistor paste, and an electronic component having the resistor will be described.

The conductive material of the present invention contains a Ru-based composite oxide whose basic composition is represented by A _(x) RuO ₃ (wherein A is an arbitrary element), and 0 <x <1. It is. In the Ru-based composite oxide used in the present invention, the abundance ratio x of the arbitrary element A is set within the range of 0 <x <1, that is, compared to the conventional Ru-based composite oxide (x = 1). It is important to reduce the abundance ratio of the optional element A. If the ratio x of the optional element A is zero, RuO _{2 is obtained} . Conversely, if the ratio of the optional element A is 1 or more, the composition is the same as that of the conventional Ru-based composite oxide, so both TCR characteristics and STOL characteristics are achieved. Is difficult.

In the Ru-based composite oxide, for example, by setting the optional element A to at least one selected from Ca, Sr, Ba and the like, resistance equivalent to Pb ₂ Ru ₂ O _{6 and the} like conventionally used for high resistance applications A conductive material having a rate can be obtained.

Next, the manufacturing method of the electroconductive material of this invention is demonstrated. The conductive material as described above is basically prepared by mixing a predetermined amount of a compound containing the optional element A and RuO ₂ as a raw material for the Ru-based composite oxide, and firing the mixture. Can be produced.

When adjusting the mixture before firing, the ratio x of the optional element A in the Ru-based composite oxide whose basic composition is represented by A _(x) RuO ₃ is within the range of 0 <x <1 with respect to Ru. Therefore, when the amount of the arbitrary element A in the compound containing the arbitrary element A is X mol and the amount of the RuO ₂ is Y mol, X and Y are in a ratio of 0 <X <Y = 1. A mixture is prepared.

When the optional element A in the Ru-based composite oxide is at least one selected from Ca, Sr, and Ba, examples of the compound containing the optional element A that is a raw material of the Ru-based composite oxide include CaCO ₃ , SrCO ₃ , It is preferable to use at least one such as BaCO ₃ .

  Moreover, it is preferable that the calcination temperature which bakes a raw material mixture shall be 900 to 1400 degreeC. If the firing temperature is below the above range, the firing may not proceed sufficiently and the characteristics may be insufficient. Conversely, if the firing temperature is above the above range, the composite oxide may be decomposed.

In addition, the method for producing the conductive material of the present invention is not limited to the above-described method. For example, a final composition of an AruO ₃ powder, which is a kind of Ru-based composite oxide, and a RuO ₂ powder is used. It is also possible to simply mix at a ratio such that is A _(x) RuO ₃ (where 0 <x <1). However, the method of firing after preparing the mixture so that the ratio of the optional element A (X mole) and Ru (Y mole) satisfies the relationship of 0 <X <Y = 1 before firing as described above is 10 kΩ. It is extremely effective in that a Ru-based composite oxide suitable as a conductive material can be obtained with both a high resistance of □ or more and a TCR characteristic and a STOL characteristic.

  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-based composite oxide is used as the conductive material. The content of the conductive material in the resistor paste is 9.4 wt% to 53.3 wt% when the total weight of the glass composition, the conductive material, and the additive is 100 wt%. Is preferred. When the content of the conductive material is less than the above range, the resistance value becomes too high, which may make it unsuitable for use as a resistor paste. On the contrary, 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 weight or less). Lead may be contained in a trace amount as an inevitable impurity.

When the glass composition is a resistor, it has a role of binding the conductive material and the additive to the substrate in the resistor. The glass composition can be used by mixing a modified oxide component, a network-forming oxide component, or the like as a raw material. Examples of the main modifying oxide component include alkaline earth oxides, specifically, at least one selected from CaO, SrO, and BaO. Examples of the network forming oxide component include B ₂ O ₃ and SiO ₂ . In addition to the main modified oxide component, any other metal oxide can be used as another modified oxide component. Specific metal oxides, for example _{ZrO 2, Al 2 O 3,} ZnO, CuO, NiO, CoO, MnO, Cr 2 O 3, V 2 O 5, MgO, Li 2 O, Na 2 O, K 2 O , TiO ₂ , SnO ₂ , Y ₂ O ₃ , Fe ₂ O _3, etc., among which at least one selected from ZrO ₂ , Al ₂ O ₃ , and MnO is preferable.

  There is an optimum range for the content of each component in the glass composition. For example, if the content of the main modifying oxide component is too small, the reactivity with the conductive material is lowered and the TCR and STOL characteristics are deteriorated. There is a fear. On the other hand, when the content of the main modifying oxide component is too large, when a resistor is formed, excessive metal oxide may be deposited, which may deteriorate the characteristics and reliability. When the content of the network-forming oxide component is small, the softening point of the glass composition becomes high. Therefore, when a resistor is formed at a predetermined firing temperature, the resistor is not sufficiently sintered and the reliability is remarkably improved. May decrease. On the other hand, when the content of the network-forming oxide component is too large, the water resistance of the glass composition is lowered, and thus there is a possibility that the reliability when a resistor is used is significantly lowered. Moreover, when there is too little content of another modification oxide component, since the water resistance of a glass composition falls, there exists a possibility that the reliability when it may be set as a resistor may fall remarkably. On the other hand, when the content of other modified oxide components is too large, when a resistor is formed, excessive metal oxide may be deposited, which may deteriorate the characteristics and reliability.

  The content of the glass composition in the resistor paste is 47.7 wt% to 90.6 wt% when the total weight of the conductive material, the glass composition, and the additive is 100 wt%. preferable. When the content is small, 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, which may make it unsuitable for use as a resistor paste.

  In addition to the glass composition and the conductive material 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 0 to 27.2% by weight when the total weight of the glass composition, the conductive material, and the additive is 100% by weight. It is more preferable to set it as weight%-27.2 weight%. When the content of the additive is small, it is difficult to sufficiently adjust the characteristics. 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, like _{MgO, TiO 2, SnO 2,} ZnO, CoO, CuO, NiO, MnO, Mn 3 O 4, Fe 2 O 3, Cr 2 O 3, Y 2 O 3, V 2 O 5 and the like It is done. Among these, CuO, NiO, and MgO, which are highly effective oxides as a TCR adjuster, are preferable. When there is too much content of each additive, there exists a possibility that a STOL characteristic may deteriorate.

  The organic vehicle has a role of kneading the glass composition, the conductive material, 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 terpineol, 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 weight (W1) of the glass composition, the conductive material, and the additive to the weight (W2) of the organic vehicle (0.25). -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, and this conductive pattern is printed with a conductive paste containing an Ag-based highly conductive material containing Ag, Pt, Pd, or the like, for example. Can be formed. Further, a protective film such as a glass film may be formed on the surface of the formed resistor.

  The electronic component to which the resistor of the present invention can be applied is not particularly limited. For example, a single-layer or multi-layer circuit board, a resistor such as a chip resistor, an isolator element, a CR composite element, a module element, and a laminated layer Capacitors such as chip capacitors, inductors and the like can be mentioned, and the present invention can also be applied to electrode portions such as capacitors and inductors.

  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 to which the present invention is applied will be described based on experimental results. Needless to say, the present invention is not limited to the following examples.

<Production of conductive material>
A ratio of Ca, Sr, and Ba as the optional element A in a Ru-based perovskite type complex oxide having a basic composition of A _(x) RuO ₃ (wherein A represents an optional element). Predetermined amounts of CaCO ₃ , SrCO ₃ , BaCO ₃ powder and RuO powder were weighed so that x was x = 0.5 to 1.0, mixed in 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 to obtain Sample A to Sample H. Sample I was a powder obtained by pulverizing RuO ₂ used as a raw material. Further, RuO ₂ (conductive material I) used as a raw material and CaRuO ₃ (conductive material A) were mixed at a molar ratio of 1: 1, and pulverized to obtain Sample J. The obtained conductive material (Ru-based composite oxide) is shown in Table 1.

<Preparation of glass composition>
A predetermined amount of a compound such as B ₂ O ₃ , SiO ₂ , CaCO ₃ , BaCO ₃ , ZrO ₂ , Al ₂ O ₃ was 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.

<Conductive materials and additives>
As an additive, CuO, NiO, MgO or the like was used.

<Preparation 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 above-mentioned conductive material powder, glass composition powder, additive, and 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 weight of the conductive material powder, the glass composition powder and the additive powder to the weight of the organic vehicle is 1: 1 by weight 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.

<Fabrication 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 weight, and the Pt ratio was 5% by weight. 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.

<Evaluation of resistor characteristics>
(1) Resistance value
Measured with Agilent Technologies product number 34401A. The average value of 24 samples was determined.

(2) TCR
The resistance value change rate when the temperature was changed to −55 ° C. and 125 ° C. was obtained based on the room temperature of 25 ° C. The average value of 10 samples. TCR (ppm / ° C) = [(R-55-R25) / R25 / 80] x resistance values of -55 ° C, 25 ° C, 125 ° C are R-55, R25, R125 (Ω / □) 1000000, or TCR (ppm / ° C.) = [(R125−R25) / R25 / 100] × 1000000. The larger value was taken as the TCR value.

(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.

(4) Constant temperature and humidity load test This is one of the reliability tests of resistors. While applying a voltage of 15 V to the resistor, it was left in an atmosphere having a temperature of 85 ° C. and a relative humidity of 85%, and the resistance value fluctuation after 1000 hours was evaluated. When the resistance value fluctuation before and after the test is ΔR (%), it is preferably ± 1.0% or less.

<Examination of Arbitrary Element A of Conductive Material>
Samples 1 to 9 were prepared using the samples A to I as conductive materials, and the characteristics of the resistor (resistance value, TCR, STOL, constant temperature and humidity load test) were evaluated. Table 3 shows the evaluation results of the resistor paste composition and resistor characteristics. 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 *.

From Table 3, samples 2, 3, 4, 6, using a conductive material in which x in the range of 0 <x <1 in the Ru-based composite oxide whose basic composition is represented by A _(x) RuO ₃ , 8 is improved in both TCR characteristics and STOL characteristics as compared with Samples 1, 3, and 8 in which x = 1. Also in the constant temperature and humidity load test, the resistance value fluctuation ΔR is small. On the other hand, the sample 9 using RuO ₃ (x = 0) as the conductive material has remarkably deteriorated STOL characteristics and a large resistance value variation ΔR.

<Examination of manufacturing method of conductive material>
Although represented by the same basic composition as that of the conductive material D (Ca _(0.5) RuO ₃ ), the sample 10 was manufactured using the conductive material J manufactured by a different manufacturing method, and the characteristics of the resistor were evaluated. The evaluation results of the composition and characteristics of the resistor paste of Sample 10 are shown in Table 4 together with the evaluation results of the composition and characteristics of Sample 4 using the conductive material D alone.

From Table 4, even if the basic composition of the conductive material (Ru-based composite oxide) is the same, the sample 4 using the conductive material D that was fired after adjusting the composition was the Ru-based composite after firing. The STOL characteristics are greatly improved as compared with the sample 10 using the conductive material J in which an oxide and RuO ₂ are simply mixed.

<Examination of glass composition>
Samples 11 to 18 were prepared by changing the glass composition as shown in Table 5, and the characteristics of the resistors were evaluated. Table 5 shows the evaluation results of the composition and characteristics of the resistor pastes of Samples 11 to 18.

From Table 5, when any glass composition is used, a sample in which x is less than 1 in a Ru-based composite oxide whose basic composition is represented by A _(x) RuO ₃ , and a sample in which x is 1 From the above comparison, by using as a conductive material a Ru-based composite oxide in which x is 0 <x <1 in a Ru-based composite oxide whose basic composition is represented by A _(x) RuO ₃ , TCR characteristics and STOL It can be seen that both characteristics can be improved.

<Examination of additives>
As shown in Table 6, various additives were included in the resistor paste to prepare Samples 19 to 24, and the characteristics of the resistors were evaluated. Table 6 shows the evaluation results of the composition and characteristics of the resistor pastes of Sample 19 to Sample 24.

From Table 6, when any additive is used, a sample in which x is less than 1 and a sample in which x is 1 in a Ru-based composite oxide whose basic composition is represented by A _(x) RuO ₃ From the comparison, it can be seen that good characteristics can be obtained by using a Ru-based composite oxide in which x is 0 <x <1 as the conductive material.

<Examination of mixing ratio of conductive material and glass composition>
Samples 25 to 29 were prepared by changing the mixing ratio of the conductive material and the glass composition as shown in Table 7, and the characteristics of the resistors were evaluated. Table 7 shows the evaluation results of the composition and characteristics of the resistor pastes of Sample 25 to Sample 29.

From Table 7, the resistance value becomes too high in Sample 25 in which the mixing ratio of the conductive material and the glass composition is 7.6: 92.4 by weight, whereas in Sample 27 and Sample 29, Sample 28 using a Ru-based composite oxide having an appropriate resistance value of 10 kΩ / □ or more and having a basic composition represented by A _(x) RuO ₃ as x being x = 1 as a conductive material In addition, both TCR characteristics and STOL characteristics can be achieved as compared with the sample 30. Accordingly, when the total weight of the glass composition and the conductive material in the resistor paste is 100, the ratio of the glass composition is 47.7% to 90.6%, and the ratio of the conductive material is It turns out that it is preferable to set it as the range of 9.4%-53.3%.

Claims (18)

A conductive material having a basic composition represented by A _(x) RuO ₃ (wherein A is an arbitrary element) and containing a Ru-based composite oxide where 0 <x <1.   The conductive material according to claim 1, wherein the arbitrary element A is at least one selected from Ca, Sr, and Ba. The Ru-based composite oxide includes a compound containing the optional element A so that the ratio 0 <X <Y = 1 when the amount of the optional element A is X mol and the amount of RuO ₂ is Y mol. The conductive material according to claim 1, wherein the mixture is obtained by baking a mixture of RuO ₂ and RuO ₂ . A mixture in which a predetermined amount of a compound containing the optional element A and RuO ₂ is mixed is fired, and the basic composition is represented by A _(x) RuO ₃ (where A is an optional element), and 0 <x When producing a Ru-based composite oxide that is <1,
When the amount of the arbitrary element A is X mol and the amount of the RuO ₂ is Y mol, the compound containing the arbitrary element A and the compound so that the ratio of 0 <X <Y = 1 in the mixture A method for producing a conductive material, comprising mixing RuO ₂ .   The method for producing a conductive material according to claim 4, wherein the arbitrary element A is at least one selected from Ca, Sr, and Ba. The method for producing a conductive material according to claim 4, wherein the compound containing the arbitrary element A is at least one selected from CaCO ₃ , SrCO ₃ , and BaCO ₃ .   The method for producing a conductive material according to claim 4, wherein the baking is performed at 900 ° C. to 1400 ° C. A resistor paste containing a glass composition and a conductive material, which is mixed with an organic vehicle,
The conductive material contains a Ru-based composite oxide in which a basic composition is represented by A _(x) RuO ₃ (wherein A is an arbitrary element), and 0 <x <1. A resistor paste.   The resistor paste according to claim 8, wherein the A is at least one selected from Ca, Sr, and Ba. The Ru-based composite oxide includes a compound containing the optional element A so that the ratio 0 <X <Y = 1 when the amount of the optional element A is X mol and the amount of RuO ₂ is Y mol. The resistor paste according to claim 8, wherein the mixture is made by firing a mixture of bismuth and RuO ₂ .   The resistor paste according to claim 8, further comprising an additive.   The resistor paste according to claim 11, wherein the additive is at least one selected from CuO, NiO, and MgO.   When the total weight of the glass composition, the conductive material, and the additive is 100, the ratio of the glass composition is 47.7% to 90.6%, and the ratio of the conductive material is 9. The resistor paste according to claim 8, wherein 4% to 53.3% and the ratio of the additive is 0 to 27.2%. The glass composition is at least one selected from CaO, SrO and BaO as a main modifying oxide component;
The resistor paste according to claim 8, comprising at least one selected from B ₂ O ₃ and SiO ₂ as a network-forming oxide component. The resistor paste according to claim 14, wherein the glass composition contains at least one selected from ZrO ₂ , Al ₂ O ₃ , and ZnO as another modified oxide component.   The ratio of the total weight of the glass composition, the conductive material, and the additive to the weight of the organic vehicle is 1: 0.25 to 1: 4. Resistor paste.   A resistor formed using the resistor paste according to any one of claims 8 to 16.   An electronic component comprising the resistor according to claim 17.