JPH0590005A - Thick film resistor composition, electric resistance element paste using the same, and methods for producing the same - Google Patents

Abstract

(57) [Summary] [Purpose] A composition for thick film resistors containing ruthenium oxide as a main composition and a thick film resistor for electric resistance elements, so that the resistors can be fired in a stable state even under low oxygen partial pressure. A body paste and methods for making the same are provided. [Constitution] The conductive powder, which is a double oxide of a perovskite type compound composed of Ce oxide and Ru oxide, is 20 to 70.
% By weight, non-reducing glass frit 30-80
Wt% composition for thick film resistor, Ce oxide and Ru
100% by weight of the composition for a thick film resistor in which the conductive powder, which is a complex oxide of a perovskite type compound composed of an oxide, is 20 to 70% by weight and the non-reducing glass frit is 30 to 80% by weight. And a paste for an electric resistance element, which is composed of 20 to 40 parts by weight of a component dispersion spreader composed of a resin and a solvent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thick film resistor composition for producing an electric resistance element as a resistor for a hybrid IC using a Cu electrode or a thick film resistor for a thick film chip resistor. The present invention also relates to a paste for an electric resistance element using the paste and a method for manufacturing these.

[0002]

2. Description of the Related Art Conventionally, as a composition for a thick film resistor for producing an electric resistance element as a resistor for a hybrid IC or a thick film resistor for a thick film chip resistor, Au or Ag has been known.
A ruthenium oxide-based thick film resistor paste such as RuO ₂ or Bi ₂ Ru ₂ O ₆ together with a noble metal-based thick film conductor composed of a Pd alloy or the like on an insulating substrate such as an alumina substrate; For example, after a circuit pattern is drawn using a screen printing method, this is printed in the atmosphere and used.

The thick film resistor paste used in this case has a raw material powder as a conductive powder, a glass frit as an inorganic binder, and a component dispersion spreader as its constituent components. After being sufficiently mixed, a three-roll mill or the like is used to further perform a kneading process for a long time to form a paste.

The component dispersion extender used in this case is composed of a resin as a binder and a solvent for the resin.

However, at the present time when electronic circuits have been miniaturized and integrated with each other, the resistivity is low as a resistor for a hybrid IC or an electrode material for a thick film chip resistor, and migration is less than that of an Ag system. Attention is being paid to the practical application of a Cu conductor, which is low in degree and excellent in solder wettability, and further contributes to cost reduction.

As described above, while showing some advantages possessed as its characteristics, when actually using the Cu conductor, the circuit pattern drawn on the substrate is fired to obtain a thick film resistor. In order to prevent the Cu conductor from being oxidized in the finishing step, it is necessary to proceed with the work under a low oxygen partial pressure.

However, when the work is advanced under a low oxygen partial pressure, a part or most of the ruthenium oxide-based resistor exhibiting a high performance is actually reduced to a metal Ru, It was often difficult to obtain a predetermined resistance characteristic.

In order to eliminate such inconvenience, the ruthenium oxide-based resistor is fired in the atmosphere at a temperature higher than 900 ° C., and then Cu is placed in an inert atmosphere at a temperature of about 600 ° C.
A proposal was made for commercialization by adopting a two-step firing method for forming a conductor.

At first glance, this method seems to be a practical method. However, when this method is adopted, in reality, a contact failure easily occurs between the ruthenium oxide resistor and the Cu conductor. In order to fully utilize the excellent conductivity of the Cu conductor, the firing temperature of the Cu conductor of 600 ° C is insufficient, and in order to utilize the inherent high conductivity of the Cu conductor, a non-oxidizing atmosphere of about 900 ° C is used. The advent of resistors that enable the firing process inside has been urgently required.

In such a situation, LaB ₆ system, Ta
-TaN system, the raw material powder of SnO ₂ based and conductor particles 90
A resistor that can be fired together with a Cu conductor at about 0 ° C. has been devised, and partly put to practical use.

However, in this case as well, since the conductive particles which are the boron compound or the nitride which is the constituent composition thereof do not have sufficient wettability with the glass component which is the same constituent composition, the conductive particles which form the main part of the conductor. However, as expected, it often causes a phenomenon in which it is difficult to disperse, and this results in deteriorating the noise characteristic which is also a part of the basic characteristic of the resistor obtained by the baking treatment.

Further, in this case, the boron compound or nitride used as the raw material is not easy to produce by the usual wet chemical method, and much more, the average particle diameter required for the conductive particles is 0. Obtaining fine particles having a size of 5 μm or less has to be quite difficult, and inevitably, a ball mill,
Although there is no choice but to rely on mechanical crushing treatment with a stamp mill etc., the hardness is extremely high if the object is a boron compound or nitride, so processing to obtain fine powder is almost impossible. As a result, it was unavoidable that the processing cost soared only by jet milling.

On the other hand, since the boron compound used as a raw material in this case exerts a strong reducing action, a component of the glass composition which is not reduced by the boron compound, for example, a free energy of formation is required. It has to be used only for high oxides such as alkali metal oxides, alkaline earth oxides, silicon oxide, boron oxide, etc., and the degree of freedom in selecting the composition for glass frit is extremely low. ..

All the physical properties such as the softening point, the glass transition point, the coefficient of thermal expansion, and the elastic modulus of the glass frit have a great influence on the characteristics of the resistor. Especially, when the resistor is trimmed by a laser. In addition, since the finishing degree when the resistor is trimmed is greatly affected by the above characteristics, it is said that the degree of freedom in selecting the composition for the glass frit is extremely low. That is, it is extremely difficult to improve the processing characteristics of the resistor when the resistor is trimmed with a laser.

In consideration of the above, it is possible to perform the firing treatment in the air like the existing ruthenium oxide-based ones and to show high conductivity, and further, the firing treatment with a low oxygen partial pressure so that the Cu conductor is not oxidized. Highlights the market situation in which there is a high demand for the development of a composition for resistors containing ruthenium, in which Ru is not reduced in some cases.

In JP 60-262401 A, the general formula is A
Ruthenium oxides SrRUO ₃ , BaRuO ₃ , and CaRuO, which are perovskite structures represented by BO _3.
A resistor containing an oxide having a basic composition of ₃ etc. is presented.

In this case, the ruthenium oxide having the perovskite structure is much more stable than ruthenium oxide having the rutile structure at 900 ° C. at the same time as the Cu conductor because of its large lattice energy under low oxygen partial pressure. It has the advantage that the reduction phenomenon to Ru is difficult to be performed even if the firing process is performed under a low oxygen partial pressure.

Further, the specific resistance of the resistor formed from the composition in this case is 10 ⁻³ Ω / cm to 10 ⁻⁴ Ω / c.
It is possible to adjust to a range of up to m, resulting in 10
The resistance value can be set consciously over a wide range from 0Ω / □ to 1MΩ / □.

The compositions described in the above publications are
The resistance temperature coefficient and noise characteristics of the resistor can be easily adjusted by adding various additives at the same time or by replacing the additives with the perovskite structure factor to form a solid solution. It is considered promising for the body.

However, the inventions disclosed in the above publications, which exhibit excellent performances in these respects, also tend to lack stability under low oxygen partial pressure. For example, the component dispersion in the paste during firing of the resistor is spread. R which is a part of the perovskite structure due to the reducing hydrocarbon gas generated by the burning of the agent and the carbon remaining due to the incomplete combustion.
In some cases, the reduction phenomenon of u may occur, and as a result, it becomes difficult to obtain the desired resistance value. Therefore, when heating the component-dispersed spreader, more than necessary force is required to adjust the oxygen partial pressure. However, this has the drawback of shifting to higher production costs.

[0021]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems and is a thick film resistor containing ruthenium oxide as a main composition so that a resistor can be fired in a stable state even under a low oxygen partial pressure. The purpose is to provide body paste.

[0022]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to solve the above problems, and as a result, the fact that the oxidation phenomenon of a Cu conductor is easily suppressed by using a rare earth metal The present invention has been found and has led to the disclosure of the present invention, and the details thereof will be described below.

In the present invention, the conductive powder, which is a double oxide of a perovskite type compound composed of Ce oxide and Ru oxide, is 20 to 70% by weight, and the non-reducing glass frit is 30 to 80% by weight. % Of the conductive powder, which is a composite oxide of a perovskite-type compound composed of Ce oxide and Ru oxide, is 20 to 70% by weight. 1 of a composition for a thick film resistor having a non-reducing glass frit of 30 to 80% by weight
Disclosed is a paste for an electric resistance element, which comprises 00 parts by weight and 20 to 40 parts by weight of a component dispersion spreader composed of a resin and a solvent.

The present invention also provides the above thick film resistor composition and electrical resistance element wherein the molar ratio of Ce to Ru is 0.95 to 1.05: 1.05 to 0.95. Disclose the paste.

Further, in the present invention, Ce and Ru are both raw materials in the form of metal or its oxide, chloride, hydroxide, nitrate, and sulfate, respectively, and Ce and Ru are in a molar ratio of 0. 95 to 1.05: 1.05 to 0.95, and after mixing the respective raw materials, the mixture was transferred to a refractory container and heated to 800 to 1100 ° C. in a nitrogen atmosphere or an oxidizing atmosphere. The lumps are finely pulverized to 1 μm or less to obtain conductive powder, and the final composition contains 20 to 70% by weight of the above conductive powder, SrO, SiO ₂ , B ₂ O ₃ , Al ₂ O ₃ , and Zn.
O, Ta ₂ O ₅ , Nb ₂ O ₅ , and TiO ₂ are weighed and mixed so that the non-reducing glass frit containing a plurality of substances selected from the main components is 30 to 80% by weight. Disclosed is a method for producing a composition for thick film resistors, which is a composition for thick film resistors.

In addition, according to the present invention, each of Ce and Ru is contained as a raw material in the form of a metal or its oxide, chloride, hydroxide, nitrate, or sulfate, and Ce and Ru are in a molar ratio of 0. 0.95 to 1.05: 1.05 to 0.95, and then transfer to a refractory container and heat to 800 to 1100 ° C. in a nitrogen atmosphere or an oxidizing atmosphere. The pulverized lumps are finely pulverized to prepare conductive powder having an average particle size of 1 μm or less.
0-70 _{wt%, SrO, SiO 2, B} 2 O 3, Al 2
A composition of 30 to 80% by weight of a non-reducing glass frit containing a plurality of substances selected from O ₃ , ZnO, Ta ₂ O ₅ , Nb ₂ O ₅ , and TiO ₂ as a main component is used. It is prepared by further mixing 100 parts by weight of this composition with 20 to 40 parts by weight of a component dispersion spreading agent composed of a resin and a solvent, and then kneading the mixture for a longer period of time. Disclosed is a method for manufacturing an electric resistance element paste.

[0027]

In the present invention, the double oxide of the perovskite type compound composed of Ru oxide is used because the perovskite type compound has a larger lattice energy than the rutile type compound which is usually used. This is because it is much more stable at a low oxygen partial pressure, and even if the Cu conductor is fired at a low oxygen partial pressure of about 900 ° C. in parallel with the firing treatment, Ru is not reduced and produced. ..

In the present invention, the conductive powder, which is a double oxide of a perovskite type compound composed of Ce oxide and Ru oxide, is 20 to 70% by weight, and the non-reducing glass frit is 30 to 80% by weight. The composition ratio of the conductive powder in the thick film resistor composition is set to 20 to 70% by weight because the composition ratio of the conductive powder is 20% by weight. If it is less than 100%, the film strength of the resistor film itself generated is not sufficient, and conversely, if the composition ratio of the conductive powder exceeds 70% by weight, the adhesive strength between the resistor film and the substrate becomes insufficient. Is.

In the present invention, the conductive powder, which is a double oxide of a perovskite type compound composed of Ce oxide and Ru oxide, is 20 to 70% by weight, and the non-reducing glass frit is 30 to 80% by weight. 100 of the composition for thick film resistor which is
The weight of the component dispersion spreader composed of the resin and the solvent and 20 to 40 parts by weight of the component dispersion spreader is the weight of the component dispersion spreader in the paste for the electric resistance device. If the ratio is less than 20 parts by weight, the spreadability as an electric resistance element paste will be poor, and it will be difficult to draw the desired pattern. Conversely, if the weight ratio of the component dispersion spreader is This is because if the amount exceeds 40 parts by weight, the electric resistance element paste will easily flow, and it will be difficult to draw the desired pattern sufficiently.

In the present invention, Ce and R of the thick film resistor composition are used.
u and the molar ratio are 0.95 to 1.05: 1.05 to 0.9
The respective raw materials were blended so as to be 5 because the reduction phenomenon of Ru is easily recognized when the molar ratio of Ce is less than 0.95, and when it exceeds 1.05, the composition for thick film resistors is This is because the required amount of Ru that constitutes the electric resistance element paste is reduced, and it is likely that the predetermined performance held by each of them will not be satisfied.

In the present invention, the non-reducing glass frit is used as the composition of the thick film resistor composition is PbO or C.
Inclusion of easily reduced oxides such as uO, NiO, and WO ₃ results in the reduction phenomenon of Ru, and the temperature is 900 ° C.
This is because it is difficult to obtain a sufficiently satisfactory result when firing is performed in parallel with Cu under a low oxygen partial pressure.

In the present invention, the average particle size of the conductive powder is defined to be 1 μm or less. The reason is that when the average particle size of the conductive powder exceeds 1 μm, the resistance value in each part of the resistor as a product varies. This is because it tends to occur, and as a result, it becomes difficult to supply products having satisfactory performance.

[0033]

EXAMPLES Example 1 85.5 g of CeO ₂ (produced by Rare Metallic Co., Ltd., purity 99.9%) and RuO ₂ (Sumitomo) were used so that the molar ratio of Ce and Ru was 1: 1. 66.2 g manufactured by Metal Mining Co., Ltd., purity 99.99%) was weighed, respectively, and then ethanol was used as a dispersion solvent, and both of them were mixed with a bow mill using zirconia balls having a diameter of 5 mm to form a slurry. Was transferred to a flat-bottom Teflon vat and dried at 60 ° C. for 2 hours by a drier to give a dry mixed raw material powder, which was then transferred to a platinum crucible and baked in nitrogen at 950 ° C. for 12 hours. To obtain a conductive powder.

Using the above conductive powder, a pressure of 60 kgf /
A powder compact having a diameter of 10 mm and a thickness of 2 mm was prepared in cm ² , and the powder compact was held in nitrogen at 950 ° C. for 12 hours to obtain a sample for measuring the specific resistance and the resistance change rate.

The resistance value at 25 ° C. of the conductive powder measured by the direct current 4-terminal method using the above measurement sample was 0.15.
It is 1 Ω / cm, and the resistance value at -55 ° C is 0.09.
8Ω / cm, temperature coefficient of resistance is + 4390p
It was pm.

The above green compact has an oxygen concentration of 1 × 10.
^When heat-treated in high-purity nitrogen of ^-6 atm at 1000 ° C for 1 hour and the crystalline state of the sample was analyzed by the powder X-ray method, no reduction precipitation of Ru was observed in the sample even after the heat treatment. At the same time, no dissociation phenomenon as Ru ₂ O was observed.

The conductive powder obtained as described above has an internal volume of 20.
The powder was transferred to a 0 cc ball mill, and zirconia balls with a diameter of 5 mm were pulverized with ethanol as a dispersion solvent for 12 hours to obtain conductive powder. The particle size of the conductive powder was measured by a scanning electron microscope. Diameter is 0.5
was μm.

30 g of the above-mentioned conductive powder having an average particle size of 0.5 μm, an average particle size of 3 μm, and an SrO content of 40 g.
% By weight, B ₂ O ₃ by 30% by weight, Al ₂ O
₃ is 5% by weight, SiO ₂ is 15% by weight, Z
70 g of a glass frit having a glass composition C in which nO was 5% by weight, TiO ₂ was 2.5% by weight, and Ta ₂ O ₅ was 2.5% by weight, terpineol was used as a solvent, and ethylcellulose was used as a resin. Ingredient dispersion spreader 3
3 g was weighed and mixed on a plate glass, and this mixture was kneaded with a three-roll mill for 12 hours to obtain a paste for an electric resistance element.

Using this paste, a specific pattern having a film thickness of 40 μm was formed on an alumina substrate on which a Cu electrode was previously formed, subjected to leveling treatment for 30 minutes, and then dried at 120 ° C. for 10 minutes. Furthermore, the dried product was transferred to a binder removal process at 430 ° C. for 1 hour using a belt conveyor furnace under a nitrogen atmosphere, and finally, a baking process was performed at 900 ° C. for 10 minutes. , 1 for the entire heating cycle, including the subsequent cooling operation
The respective test data when the physical property test was carried out on the resistor obtained in a timed manner showed the following numerical values.

That is, the resistance value is 192 × 10 ⁶ Ω / □, and the resistance values measured at the temperatures of −55 ° C., 25 ° C. and 125 ° C. are R ₋₅₅ , R ₂₅ and R ₁₂₅ , respectively. if you did this,
(R ₋₅₅ −R ₂₅ ) / − 80R ₂₅ × 10 ⁶ ppm / ° C, the cold temperature coefficient (CTCR) is −191 ppm / ° C.
And (R ₁₂₅ -R ₂₅ ) /-100R ₂₅ × 10 ⁶ pp
Temperature coefficient at heat (HTCR) expressed in m / ° C is -130.
It was ppm / ° C.

As an electrostatic withstand voltage test, an initial resistance value was set to R ₀ Ω / □ under an applied voltage of 1 Kv, and a time interval was set to 10.
When the resistance value after applying 5 times at 00 ms is R _x , the resistance value change rate (ΔR) represented by ((R _x −R ₀ ) / R ₀ ) × 100% is −5.5%. It was

(Example 2) The composition ratio of the conductor powder was 45% by weight, SrO was 45% by weight, B ₂ O ₃ was 20% by weight, and Al ₂ O ₃ was 5% by weight as a glass frit. 20% by weight of SiO ₂ and 5% of ZnO
Glass composition A in which the amount of TiO ₂ is 5% by weight.
When the glass frit described above was used and the treatment was carried out in the same manner as in Example 1 except that the composition ratio of the glass frit was set to 55% by weight, the following numerical values were obtained as the measured values.

That is, the resistance value is 21 × 10 ⁶ Ω / □, and the resistance values measured at the temperatures of −55 ° C., 25 ° C. and 125 ° C. are R ₋₅₅ , R ₂₅ and R ₁₂₅ , respectively. if you did this,
_{(R -5 5 -R 25) /} - when cold temperature coefficients indicated by ^{_{80R 25 × 10 6 ppm / ℃}} (CTCR) is -145ppm / ℃
And (R ₁₂₅ -R ₂₅ ) /-100R ₂₅ × 10 ⁶ pp
Temperature coefficient at heat (HTCR) in m / ° C is -150
It was ppm / ° C.

In the electrostatic withstand voltage test, the initial resistance value was set to R ₀ Ω / □ under an applied voltage of 1 Kv, and the time interval was set to 10.
When the resistance value after applying 5 times at 00 ms is R _x , the resistance value change rate (ΔR) represented by ((R _x −R ₀ ) / R ₀ ) × 100% is −3.7%. It was

(Example 3) The molar ratio of Ce to Ru was 0.9.
CeO ₂ (manufactured by Rare Metallic Co., Ltd., purity 99.9%) and 80.0 g of RuO so that the ratio becomes 7: 1.03.
₂ (Manufactured by Sumitomo Metal Mining Co., Ltd., purity 99.99%) 6
The composition ratio of the conductor powder obtained by weighing 5.8 g was 60% by weight, and the glass frit was 45% by weight of SrO.
And B ₂ O ₃ is 20% by weight and Al ₂ O ₃ is 5%.
% By weight, SiO ₂ by 20% by weight, ZnO by 5% by weight, and TiO ₂ by 5% by weight, a glass frit named glass composition A was used, and the composition ratio of this glass frit was 40 parts by weight. When treated in the same manner as in Example 1 except for the above, the following numerical values were obtained as the measured values.

That is, the resistance value is 7.6 × 10 ⁶ Ω / □, and the respective resistance values measured at the temperatures of −55 ° C., 25 ° C. and 125 ° C. are R ₋₅₅ , R ₂₅ and R ₂₅ , respectively. _{If it is 125} ,
(R ₋₅₅ −R ₂₅ ) / − 80R ₂₅ × 10 ⁶ ppm / ° C, the cold temperature coefficient (CTCR) is +210 ppm / ° C.
And (R ₁₂₅ -R ₂₅ ) /-100R ₂₅ × 10 ⁶ pp
Temperature coefficient at heat (HTCR) in m / ° C is +320
It was ppm / ° C.

As an electrostatic withstand voltage test, an initial resistance value was set to R ₀ Ω / □ under an applied voltage of 1 Kv, and a time interval was set to 10.
When the resistance value after applying 5 times at 00 ms is R _x , the resistance value change rate (ΔR) represented by ((R _x −R ₀ ) / R ₀ ) × 100% is −3.8%. It was

(Example 4) The molar ratio of Ce and Ru was 1.0.
In order to obtain 2: 0.98, 90.3 g of CeO ₂ (manufactured by Rare Metallic Co., Ltd., purity 99.9%) and RuO
₂ (Manufactured by Sumitomo Metal Mining Co., Ltd., purity 99.99%) 6
The composition ratio of the conductor powder obtained by weighing each of 7.1 g was set to 68% by weight, and the glass frit contained 45% by weight of SrO.
And B ₂ O ₃ is 20% by weight and Al ₂ O ₃ is 5%.
% By weight, SiO ₂ by 20% by weight, ZnO by 5% by weight, TiO ₂ by 3% by weight, Nb ₂ O
_When a glass frit called glass composition B in which ₃ is 2% by weight was used and the treatment was carried out in the same manner as in Example 1 except that the composition ratio of this glass frit was 32% by weight, the measured values were as follows. A number was obtained.

That is, the resistance value is 2 × 10 ⁶ Ω / □,
When the resistance values measured at temperatures of −55 ° C., 25 ° C., and 125 ° C. are R ₋₅₅ , R ₂₅ , and R ₁₂₅ , (R
_-55 -R ₂₅₎ / - when cold temperature coefficients indicated by ^{_{80R 25 × 10 6 ppm / ℃}} (CTCR) is _{+ 451ppm / ℃, (R 125} -R 25) / - 100R 25 × 10 6 ppm /
Temperature coefficient at heat (HTCR) expressed in ° C is + 622pp
It was m / ° C.

As an electrostatic withstand voltage test, an initial resistance value was set to R ₀ Ω / □ under an applied voltage of 1 Kv, and a time interval was set to 10.
When the resistance value after applying 5 times at 00 ms is R _x , the resistance value change rate (ΔR) represented by ((R _x −R ₀ ) / R ₀ ) × 100% is −2.3%. It was

(Example 5) The molar ratio of Ce and Ru was 1.0.
5: 0.95, CeO ₂ (manufactured by Rare Metallic Co., Ltd., purity 99.9%) and 93.9 g of RuO
₂ (Manufactured by Sumitomo Metal Mining Co., Ltd., purity 99.99%) 6
The composition ratio of the conductor powder obtained by weighing 6.0 g was 80% by weight, and the glass frit contained 45% by weight of SrO.
And B ₂ O 3 is 20% by weight and Al ₂ O ₃ is 5%.
% By weight, SiO ₂ by 20% by weight, ZnO by 5% by weight, TiO ₂ by 3% by weight, Nb ₂ O
_When a glass frit called glass composition B in which ₃ was 2% by weight was used and the treatment was carried out in the same manner as in Example 1 except that the composition ratio of this glass frit was 20% by weight, the measured values were as follows. A number was obtained.

That is, the resistance value is 1.2 × 10 ⁶ Ω / □, and the respective resistance values measured at the temperatures of −55 ° C., 25 ° C., 125 ° C. are R ₋₅₅ , R ₂₅ , R. _{If it is 125} ,
(R ₋₅₅ −R ₂₅ ) / − 80R ₂₅ × 10 ⁶ ppm / ° C, the cold temperature coefficient (CTCR) is +470 ppm / 0
C., (R ₁₂₅ -R ₂₅ ) /-100R ₂₅ × 10 ⁶ p
Temperature coefficient during heat (HTCR) in pm / ° C is +68
It was 3 ppm / ° C.

As an electrostatic withstand voltage test, under an applied voltage of 1 Kv, the initial resistance value is R ₀ Ω / □, and the time interval is 10
When the resistance value after applying 5 times at 00 ms is R _x , the resistance value change rate (ΔR) represented by ((R _x −R ₀ ) / R ₀ ) × 100% is −2.5%. It was

(Comparative Example 1) 72.3 g of SrCO ₃ (produced by Rare Metallic Co., Ltd., purity: 99.9%) as a composition
And RuO ₂ (manufactured by Sumitomo Metal Mining Co., Ltd., purity 99.99
%) 67.8 g and baking treatment at 1200 ° C.
The composition ratio of the conductor powder composed of SrRuO ₃ obtained in 0 hours was 40% by weight, and as the glass frit, SrO was 45% by weight, B ₂ O ₃ was 20% by weight, and Al
₂ O ₃ is 5 wt%, SiO ₂ is 20 wt%, ZnO is 5 wt%, and TiO ₂ is 5 wt%. When treated in the same manner as in Example 1 except that the content was 60% by weight, the following numerical values were obtained as the measured values.

That is, the resistance value is 20 × 10 ⁶ Ω / □, and the resistance values measured at the temperatures of −55 ° C., 25 ° C. and 125 ° C. are R ₋₅₅ , R ₂₅ and R ₁₂₅ , respectively. if you did this,
_{(R -5 5 -R 25) /} - 80R when cold temperature coefficients indicated by ^{_{25 × 10 6 ppm / ℃ (}} CTCR) are + 2600 ppm /
C., (R ₁₂₅ -R ₂₅ ) /-100R ₂₅ × 10 ⁶ p
Temperature coefficient at heat (HTCR) in pm / ° C is +38
It was 00 ppm / ° C.

As an electrostatic withstand voltage test, under an applied voltage of 1 Kv, an initial resistance value was set to R ₀ Ω / □, and a time interval was set to 10.
When the resistance value after applying 5 times at 00 ms is R _x , the resistance value change rate (ΔR) represented by ((R _x −R ₀ ) / R ₀ ) × 100% was −22%.

(Comparative Example 2) As a composition, 95.7 g of BaCO ₃ (produced by Rare Metallic Co., Ltd., purity: 99.9%)
And RuO ₂ (manufactured by Sumitomo Metal Mining Co., Ltd., purity 99.99
%) 66.5 g and baking treatment at 1200 ° C.
The composition ratio of the conductor powder made of BaRuO ₃ obtained at 0 hours was 40% by weight, SrO was 45% by weight, B ₂ O ₃ was 20% by weight, and Al was used as a glass frit.
₂ O ₃ is 5 wt%, SiO ₂ is 20 wt%, ZnO is 5 wt%, and TiO ₂ is 5 wt%. When treated in the same manner as in Example 1 except that the content was 60% by weight, the following numerical values were obtained as the measured values.

That is, the resistance value is 11 × 10 ⁶ Ω / □, and the resistance values measured at the temperatures of −55 ° C., 25 ° C. and 125 ° C. are R ₋₅₅ , R ₂₅ and R ₁₂₅ , respectively. if you did this,
_{(R -5 5 -R 25) /} - 80R when cold temperature coefficients indicated by ^{_{25 × 10 6 ppm / ℃ (}} CTCR) are + 1800 ppm /
C., (R ₁₂₅ -R ₂₅ ) /-100R ₂₅ × 10 ⁶ p
Temperature coefficient at heat (HTCR) in pm / ° C is +32
It was 00 ppm / ° C.

As an electrostatic withstand voltage test, under an applied voltage of 1 Kv, an initial resistance value is set to R ₀ Ω / □, and a time interval is set to 10.
When the resistance value after applying 5 times at 00 ms is R _x , the resistance value change rate (ΔR) represented by ((R _x −R ₀ ) / R ₀ ) × 100% was −25%.

Comparative Example 3 As composition, 105.5 g of PbO (manufactured by Rare Metallic Co., Ltd., purity 99.9%) and RuO ₂ (manufactured by Sumitomo Metal Mining Co., Ltd., purity 99.99) were used.
%) 62.9 g, and baking treatment at 1200 ° C.
The composition ratio of the conductor powder of Pb ₂ Ru ₂ O ₇ obtained in 0 hours was set to 40% by weight, and Sr was used as a glass frit.
O is 45% by weight, B ₂ O ₃ is 20% by weight,
A glass frit named glass composition A having 5% by weight of Al ₂ O _3, 20% by weight of SiO ₂ , 5% by weight of ZnO and 5% by weight of TiO ₂ was used. When treated in the same manner as in Example 1 except that the proportion was 60% by weight, Ru was reduced and it could not be measured as a resistor.

As described above, SrRu was used as the conductor powder.
When O ₃ and BaRuO ₃ are both used, Ru precipitates, so the temperature coefficient of resistance (TCR) shows a large value in the positive direction, and when Pb ₂ Ru ₂ O ₇ is used. Was not able to measure even the resistance value, the temperature coefficient of resistance (TCR) of the present invention was reduced by one digit in all cases, and the resistance change rate (ΔR) shown in the electrostatic withstand voltage test was also the same. The result is a test in which the effectiveness of the present invention is sufficiently confirmed.

The above results are shown together in Table 1.

[0063]

[Table 1]

[0064]

As described above, according to the present invention, it is stable in a nitrogen atmosphere and has excellent temperature coefficient of resistance and withstand voltage characteristics exhibited by a resistor. Moreover, when copper is used as a conductor, Disclosed is a paste for an electric resistance element which can be used by making full use of the characteristics of copper, and a composition for a thick film resistor which is convenient for producing the paste, and a manufacturing method thereof. So there is a great deal of contribution to the industry that uses these products.

Claims (6)

[Claims] 1. A conductive powder which is a double oxide of a perovskite type compound composed of Ce oxide and Ru oxide is 20.
~ 70% by weight, 30% non-reducing glass frit
The composition for thick film resistors is characterized in that the content is -80% by weight. 2. The conductive powder, which is a double oxide of a perovskite type compound composed of Ce oxide and Ru oxide, is 20 to 20.
70% by weight, and a non-reducing glass frit of 30-
100 parts by weight of the composition for a thick film resistor, which is 80% by weight, and 20 to 20 parts by weight of a component dispersion spreader composed of a resin and a solvent.
An electric resistance element paste comprising 40 parts by weight. 3. The molar ratio of Ce to Ru is 0.95 to 1.
The composition for thick film resistors according to claim 1, wherein the composition is 05: 1.05 to 0.95. 4. The molar ratio of Ce to Ru is 0.95 to 1.
05: 1.05-0.95, The electric resistance element paste according to claim 2, characterized in that 5. Ce and Ru are both raw materials in the form of metals or their oxides, chlorides, hydroxides, nitrates, and sulfates, and Ce and Ru are in a molar ratio of 0.95 to 1.
05: 1.05 to 0.95, after mixing the respective raw materials, the mixture was transferred into a refractory container and heated to 800 to 1100 ° C. in a nitrogen atmosphere or an oxidizing atmosphere to obtain a lump of 1 μm. Finely pulverized to the following to obtain conductive powder, and the final composition contains 20 to 70% by weight of the above-mentioned conductive powder, SrO, Si
O ₂ , B ₂ O ₃ , Al ₂ O ₃ , ZnO, Ta ₂ O ₅ , N
b ₂ O ₅ and TiO ₂ composition for thick film resistor by weighing and mixing each non-reducing glass frit containing 30-80% by weight as a main component. A method for producing a composition for a thick film resistor, comprising: 6. Ce and Ru are both contained as raw materials in the form of a metal or its oxide, chloride, hydroxide, nitrate, and sulfate, and Ce and Ru are in a molar ratio of 0.95 to 0.95.
1.05: 1.05: 0.95 to 0.95 of the respective raw materials were mixed, then transferred to a refractory container and heated to 800 to 1100 ° C. in a nitrogen atmosphere or an oxidizing atmosphere to obtain a lump. Is pulverized to prepare a conductive powder adjusted to have an average particle size of 1 μm or less. 20 to 70% by weight of the above-mentioned conductive powder, SrO, SiO ₂ , B ₂ O ₃ , Al ₂ O ₃ , Zn
A composition such that 30 to 80% by weight of a non-reducing glass frit containing a plurality of substances selected from O, Ta ₂ O ₅ , Nb ₂ O ₅ , and TiO ₂ as a main component is prepared, Further, 100 parts by weight of this composition is mixed with 20 to 40 parts by weight of a component dispersion spreader composed of a resin and a solvent, and the mixture is further kneaded for a long time. And a method for manufacturing an electric resistance element paste.