WO2019059290A1 - Composition for thick film resistor, thick film resistance paste, and thick film resistor - Google Patents

Composition for thick film resistor, thick film resistance paste, and thick film resistor Download PDF

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Publication number
WO2019059290A1
WO2019059290A1 PCT/JP2018/034854 JP2018034854W WO2019059290A1 WO 2019059290 A1 WO2019059290 A1 WO 2019059290A1 JP 2018034854 W JP2018034854 W JP 2018034854W WO 2019059290 A1 WO2019059290 A1 WO 2019059290A1
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WO
WIPO (PCT)
Prior art keywords
thick film
film resistor
mass
powder
resistance value
Prior art date
Application number
PCT/JP2018/034854
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French (fr)
Japanese (ja)
Inventor
崇仁 永野
Original Assignee
住友金属鉱山株式会社
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Filing date
Publication date
Application filed by 住友金属鉱山株式会社 filed Critical 住友金属鉱山株式会社
Priority to KR1020207002658A priority Critical patent/KR20200057695A/en
Priority to CN201880060634.2A priority patent/CN111133535B/en
Publication of WO2019059290A1 publication Critical patent/WO2019059290A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06553—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of a combination of metals and oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/12—Metallic powder containing non-metallic particles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/22—Apparatus or processes specially adapted for manufacturing resistors adapted for trimming
    • H01C17/26—Apparatus or processes specially adapted for manufacturing resistors adapted for trimming by converting resistive material
    • H01C17/265—Apparatus or processes specially adapted for manufacturing resistors adapted for trimming by converting resistive material by chemical or thermal treatment, e.g. oxydation, reduction, annealing
    • H01C17/267—Apparatus or processes specially adapted for manufacturing resistors adapted for trimming by converting resistive material by chemical or thermal treatment, e.g. oxydation, reduction, annealing by passage of voltage pulses or electric current
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions

Definitions

  • the present invention relates to a thick film resistor paste used for forming a resistor such as a thick film chip resistor, a hybrid IC, or a thermal head, a composition for a thick film resistor which is the material, and a thick film.
  • the present invention relates to a thick film resistor formed using a resistor paste.
  • a resistor used for a chip resistor, a hybrid IC, a thermal head or the like is formed by printing a thick film resistor paste on a ceramic substrate and then firing it.
  • a resistor formed using such a thick film resistor paste is generally referred to as a thick film resistor because the film thickness is thicker than a resistor formed by a method such as sputtering.
  • a thick film resistor a composition having a ruthenium oxide-based conductive powder typified by ruthenium oxide as a conductive particle and a glass powder as main components is widely used.
  • ruthenium oxide-based conductive powder and glass powder are widely used as the main components of the composition for thick film resistors. They can be fired in air, and the temperature coefficient of resistance (TCR) can be close to 0 Besides being possible, it is possible to form a resistor having various resistance values in a wide range.
  • resistors having various resistance values can be formed by changing the compounding ratio of the ruthenium oxide based conductive powder and the glass powder. .
  • a desired resistance value can be obtained by adjusting the compounding ratio of the ruthenium oxide based conductive material powder and the glass powder in the composition for a thick film resistor.
  • the most common ruthenium oxide-based conductive material is ruthenium oxide (RuO 2 ) having a rutile type crystal structure, and among the types of ruthenium oxide-based conductive materials described later, the specific resistance is the lowest.
  • a combination of ruthenium oxide (RuO 2 ) powder and glass powder can generally form a resistor of 10 ⁇ 2 ⁇ ⁇ cm to 10 4 ⁇ ⁇ cm (10 ⁇ 4 ⁇ ⁇ m to 10 2 ⁇ ⁇ m).
  • ruthenium oxide-based conductors of ruthenium oxide (RuO 2 ) having a rutile crystal structure include lead ruthenate having a pyrochlore crystal structure, bismuth ruthenate, calcium ruthenate having a perovskite crystal structure, and ruthenium Strontium acid, barium ruthenate, lanthanum ruthenate and the like, all of which are oxides exhibiting metallic conductivity.
  • ruthenium oxide based conductive material for example, ruthenium oxide (RuO 2 ) having a rutile type crystal structure is obtained by roasting an amorphous ruthenium oxide compound as described in the following Patent Document 1
  • the RuO 2 particles can be coated with at least one of KOH and NaOH, roasted again, and then manufactured by a method such as washing with water, drying and the like.
  • Glass frits include lead-containing glasses such as lead borosilicate glass (PbO-SiO 2 -B 2 O 3 ) and alumina lead borosilicate glass (PbO-SiO 2 -B 2 O 3 -Al 2 O 3 ); Lead-free glasses such as borosilicate glass, alumina borosilicate glass, alkaline earth borosilicate glass, alkali borosilicate glass, zinc borosilicate glass and bismuth borosilicate glass are widely used.
  • lead-containing glasses such as lead borosilicate glass (PbO-SiO 2 -B 2 O 3 ) and alumina lead borosilicate glass (PbO-SiO 2 -B 2 O 3 -Al 2 O 3 );
  • Lead-free glasses such as borosilicate glass, alumina borosilicate glass, alkaline earth borosilicate glass, alkali borosilicate glass, zinc borosilicate
  • the thick film resistor paste is basically composed of a composition for a thick film resistor and an organic vehicle added thereto.
  • organic vehicle those obtained by dissolving a resin such as ethyl cellulose, butyral or acrylic in a solvent such as terpineol or butyl carbitol acetate are widely used.
  • various additives, dispersants, plasticizers and the like are appropriately added in order to adjust the electrical characteristics and the like of the thick film resistor.
  • the thick film resistor paste is manufactured by grinding and mixing the various materials described above using a commercially available device such as a roll mill.
  • a thick film resistor is a commercially available coating machine such as a screen printer or an ink jet between electrodes which are previously formed of Al, Au, Ag or the like on an insulating substrate such as an alumina ceramic substrate or an alumina ceramic substrate with a glaze layer.
  • the obtained thick film resistor paste is printed using the following method, and then dried and fired to form a film.
  • the deposited thick film resistor has a large variation in resistance value. Therefore, adjustment (trimming) of the resistance value is performed on the thick film resistor in order to adjust it to a desired resistance value.
  • Laser trimming is most widely adopted as a method of adjusting the resistance value.
  • laser trimming laser light such as CO 2 is directly irradiated to a part of the thick film resistor, and the heat dissolves and vaporizes a part of the thick film resistor to lose part of the thick film resistor.
  • This is a method of adjusting by narrowing the conductive path by raising a part of the thick film resistor and raising the resistance value.
  • the laser trimming is a method of locally narrowing the conductive path and adjusting the resistance value of the resistor by melting and evaporating a part of the thick film resistor as described above, the inside of the resistor can be obtained.
  • the locally generated high-resistance portion has a higher calorific value as compared to other low-resistance portions, which causes a difference in the heat generation state inside the resistor. Therefore, it is not preferable to use a thick film resistor which has been subjected to laser trimming for a print head or a thermal head used as a heating element, because the heat generation distribution may be uneven. For this reason, adjustment of the resistance value by laser trimming is not suitable for a thick film resistor used for a print head or a thermal head used as a heating element.
  • pulse trimming which adjusts the resistance value by applying an electric load to the thick film resistor
  • the electrical load here refers to the load given by voltage and current.
  • Pulse trimming is a method in which the resistance value is varied and adjusted by applying a higher voltage than when using the product between the electrodes of a thick film resistor, and when a voltage is applied, the resistance is adjusted according to the magnitude of the voltage. It is a method that utilizes the property of a thick film resistor whose value changes, and the resistance value is often low.
  • the pulse trimming is a method of adjusting the resistance value of the thick film resistor which is very effective particularly for the recent miniaturization and high definition of fine electronic components.
  • Techniques relating to adjustment of the resistance value of a thick film resistor using pulse trimming are disclosed, for example, in the following Patent Documents 2 to 4.
  • Patent Document 2 discloses a method of manufacturing a thermal head in which voltage pulse trimming is performed once, heating is performed at a constant temperature for a predetermined time, and voltage pulse trimming is performed again.
  • Patent Document 3 discloses a method of finely adjusting the resistance value of the thermal head by applying a voltage pulse as necessary through a probe whose resistance value has been measured after performing voltage pulse trimming. It is done.
  • Patent Document 4 discloses a method of adjusting a resistance value in which a voltage is applied in a first direction to a pair of electrodes, and then a voltage is applied in a second direction opposite to the first direction. It is disclosed.
  • the method of adjusting the resistance value of the thick film resistor by such pulse trimming does not change the shape of the resistor, so that the thick film resistance having a uniform resistance value distribution in the resistor body
  • This method is suitable for adjusting the resistance value of a thick film resistor for a print head or a thermal head because it can obtain a body. Specifically, the relationship between the applied voltage of the thick film resistor subject to resistance value adjustment and the change amount of the resistance value is confirmed in advance, and the adjustment of the resistance value is performed when adjusting the resistance value.
  • the resistance value is measured, and from the measured resistance value of the thick film resistor, the change amount of the resistance value required to adjust to the desired resistance value is determined, and the voltage value applied according to the determined change amount of the resistance value
  • the desired resistance value is obtained by selecting and applying to the thick film resistor.
  • JP-A-8-268722 JP 02-130156 A Japanese Patent Application Laid-Open No. 05-305722 Japanese Patent Application Laid-Open No. 2004-247398
  • the change amount of the resistance value adjustable by one pulse trimming is the thick film resistor used, the thick film resistor paste
  • the influence of the composition of the The adjustment of the resistance value using the adjustment method by pulse trimming is different from the adjustment by raising the resistance value like the adjustment of the resistance value using the adjustment method by laser trimming, but the adjustment may be performed by lowering the resistance value. Since there are many, it is necessary to form a thick film resistor so as to be higher than a desired resistance value. Then, in consideration of the dispersion of the resistance value of the thick film resistor to be formed, it is general to form the thick film resistor by designing so that the resistance value becomes considerably higher than the desired resistance value.
  • the number of times of application may be significantly increased, and the productivity is lower than that of laser trimming, etc. If the reduction width to the resistance value is too large, it may be difficult to lower the resistance value to a desired resistance value.
  • the resistance value before trimming is designed to be a lower resistance value so that the desired resistance value can be reliably lowered. It is conceivable to form a thick film resistor, but if the thick film resistor is designed to have a lower resistance value close to the desired resistance value of the final target, the resistance value is lower than the desired resistance value. The rate at which the thick film resistor is formed is increased, and the yield may be deteriorated.
  • the present invention has been made in view of the above-mentioned conventional problems, and a thick film resistance having a large reduction rate of resistance value as a change amount of resistance value adjustable using an adjustment method by pulse trimming at the time of forming a resistor. It is an object of the present invention to provide a body composition, a thick film resistor paste and a thick film resistor.
  • the present inventor added 16 wt% of a composition for a thick film resistor to a ruthenium oxide based conductive powder comprising a mixed powder of ruthenium oxide and lead ruthenate.
  • the resistance that can be adjusted using the adjustment method by pulse trimming by using a composition containing silver powder of at least 33% by mass the rate of decrease in resistance value, which is the amount of change in value, can be increased, and the present invention has been completed.
  • the composition for a thick film resistor according to the present invention comprises 16 mass% or more of a composition for a thick film resistor containing a ruthenium oxide conductive powder comprising a mixed powder of ruthenium oxide and lead ruthenate and a glass frit. Adjustment is carried out using a pulse trimming method in a thick film resistor when a thick film resistor is formed by sintering a thick film resistor paste further containing silver powder of not more than% by mass and adding an organic vehicle It is characterized in that the reduction rate of the possible resistance value is made larger than 5%.
  • the average particle diameter of the silver powder is 0.1 ⁇ m to 5 ⁇ m, and the average particle diameter of the ruthenium oxide-based conductive powder is 1 nm to 500 nm.
  • the average particle diameter of the glass frit is preferably 0.1 ⁇ m to 5 ⁇ m.
  • the average particle diameter of the ruthenium oxide powder is preferably 7 nm or more and 30 nm or less.
  • the average particle diameter of the lead ruthenate powder is preferably 5 nm or more and 50 nm or less.
  • the thick film resistor paste according to the present invention is characterized in that an organic vehicle is further added to the composition for a thick film resistor according to any of the above-mentioned present invention.
  • the thick film resistor paste of the present invention 10% by mass or more and 20% by mass or less of the silver powder, 5% by mass or more and 30% by mass or less in total of the ruthenium oxide conductive powder, and 15% by mass of the glass frit It is preferable that the content is in the range of 70% by mass to 70% by mass, and the balance is made of the organic vehicle.
  • the thick film resistance paste of this invention it is preferable to contain 5 mass% or more and 9.3 mass% or less in total of the said ruthenium oxide type electrically conductive powder.
  • the thick film resistor according to the present invention is characterized in that it is a sintered body of any of the above-mentioned present invention thick film resistor pastes.
  • the reduction rate of the resistance value that can be adjusted by using the adjustment method by pulse trimming be larger than 5%.
  • adjustment is possible using the adjustment method by pulse trimming at the time of forming a resistor, compared to a thick film resistor formed using a thick film resistor paste containing no silver powder, which is generally used widely in the prior art Composition of a thick film resistor capable of increasing the reduction rate of the resistance value as the change amount of the resistance value, shortening the number of times and time required for pulse trimming, and improving the productivity of the resistor , A thick film resistor paste and a thick film resistor are obtained.
  • the thick film resistor paste of the present invention the composition for a thick film resistor which is the material thereof, and the thick film resistor formed by using the thick film resistor paste will be described in detail.
  • Silver powder Silver is an essential element to increase the amount of change in resistance (the rate of decrease in resistance) that can be adjusted using the adjustment method by pulse trimming in the present invention, and in the present invention, the average particle diameter is A silver powder of 0.1 ⁇ m to 5 ⁇ m is used. If the average particle size of the silver powder is less than 0.1 ⁇ m, the production cost is increased, the handling property is lowered, and the dispersibility is deteriorated due to the coarsening due to the secondary aggregation, which is not preferable. Even when the average particle size is larger than 5 ⁇ m, it is not preferable because deterioration of dispersibility occurs.
  • the silver powder to be used in the present invention is, for example, an alkali of silver nitrate once precipitated as a precipitate of silver oxide, which is reduced using a reducing agent such as sodium tetrahydroborate, hydrazine or formalin in the presence of a dispersing agent such as polyvinylpyrrolidone.
  • a reducing agent such as sodium tetrahydroborate, hydrazine or formalin
  • a dispersing agent such as polyvinylpyrrolidone.
  • the average particle size means a volume-based average particle size determined by a laser diffraction scattering method, and is a value obtained by 50% cumulative particle size by a laser diffraction scattering type particle size distribution measuring apparatus.
  • the definition of the average particle diameter also applies to a ruthenium oxide based conductive material powder and a glass frit described later.
  • the content of the silver powder may be appropriately selected according to the amount of pulse trimming, but is 16 mass% or more and 33 mass% or less with respect to 100 mass% of the composition for a thick film resistor.
  • the content of silver powder is 16% by mass or more. Even if more than 33% by mass of silver powder is contained, the rate of change is not significantly changed, and therefore it is preferable to be 33% by mass or less from the viewpoint of cost.
  • a ruthenium oxide conductive powder is used as a conductive powder for a thick film resistor.
  • a powder of ruthenium oxide (RuO 2 ) having a rutile crystal structure and a powder of lead ruthenate (Pb 2 Ru 2 O 6 ) having a pyrochlore crystal structure are used as the ruthenium oxide conductive powder.
  • the average particle diameter of the ruthenium oxide based conductive material powder is 1 nm or more and 500 nm or less. If the average particle diameter of the ruthenium oxide based conductive material powder is less than 1 nm, handling becomes very difficult and the viscosity of the thick film resistive paste becomes too high, which is not preferable.
  • the RuO 2 powder can be obtained, for example, by heat treatment of a wet synthesized hydrated RuO 2 powder. In that case, the average particle diameter of the RuO 2 powder is preferably 7 nm or more and 30 nm or less.
  • the Pb 2 Ru 2 O 6 powder can be obtained, for example, by mixing wet-synthesized Ru (OH) 4 powder and PbO powder and subjecting them to heat treatment.
  • the average particle diameter of the Pb 2 Ru 2 O 6 powder is preferably 5 nm or more and 500 nm or less.
  • the average particle diameter of the Pb 2 Ru 2 O 6 powder is 5 nm or more and 50 nm or less.
  • the content of such ruthenium oxide-based conductive material powder may be appropriately selected according to the resistance value to be formed, but the total content is 5% by mass or more and 30% by mass or less with respect to 100% by mass of the thick film resistance paste. Is preferred.
  • the inclusion of the ruthenium oxide-based conductive powder forms a conductive path in the resistor, but if the content of the ruthenium oxide-based conductive powder is less than 5% by mass, the resistance value is excessively increased, and in some cases, electricity does not flow.
  • the conductive path may be too large to obtain a sufficient resistance value, which is not preferable. More preferably, the content of the ruthenium oxide based conductive material powder is 5 mass% or more and 9.3 mass% or less in total with respect to 100 mass% of the thick film resistance paste.
  • the composition of the glass frit in the present invention is not particularly limited, and may be selected from general compositions in accordance with the composition of the dielectric sheet.
  • the average particle diameter of the glass frit is 0.1 ⁇ m to 5 ⁇ m, preferably 0.1 ⁇ m to 3 ⁇ m.
  • the average particle diameter of the glass frit is larger than 5 ⁇ m, the area resistance value of the fired thick film resistor becomes low, and the variation of the area resistance value becomes large to lower the yield or the load characteristics. It is not preferable because the possibility of problems such as lowering may increase. If the average particle size is less than 0.1 ⁇ m, the viscosity becomes too high and the handling becomes very difficult.
  • the content of such a glass frit may be appropriately selected in accordance with the resistance value to be formed, but is preferably 15% by mass to 70% by mass with respect to 100% by mass of the thick film resistor paste.
  • the resistance value of the thick film resistor can be changed by the compounding amount of the glass frit and the conductive material powder, if the content of the glass frit is less than 15% by mass, the amount of glass inhibiting the conductive path is too small. Is not preferable because it may not be able to show a sufficient resistance value.
  • the content of the glass frit exceeds 70% by mass, the resistance value is too high, and in some cases, electricity may not flow, which is not preferable.
  • the thick film resistor paste of the present invention includes conductive powder such as RuO 2 powder, glass frit, adjustment of area resistance value and temperature coefficient of resistance, adjustment of expansion coefficient, voltage resistance Additives may be added for the purpose of improvement and other modifications. It is preferable to use MnO 2 , CuO, TiO 2 , Nb 2 O 5 , Ta 2 O 5 , SiO 2 , Al 2 O 3 , ZrO 2 , ZrSiO 4 or the like generally used as an additive for thick film resistance pastes. be able to.
  • the content of the additive is not particularly limited, but is preferably 0.05 parts by mass or more and 20 parts by mass or less with respect to a total of 100 parts by mass of the RuO 2 powder and the glass frit. If the content of the additive is less than 0.05 parts by mass, the effect of the additive may hardly appear, which is not preferable. If the content of the additive exceeds 20 parts by mass, the viscosity of the thick film resistor paste may increase excessively, segregation of silver contained in the sintering process may easily occur, or the appearance resistance value of the formed resistor may be unstable. It is not preferable because it may be
  • the thick film resistor paste of the present invention contains an organic vehicle in which a resin component is dissolved in a solvent.
  • the present invention is not particularly limited by the type and composition of the resin and solvent of the organic vehicle.
  • the resin component general components such as ethyl cellulose, maleic acid resin, rosin can be used
  • the solvent component general components such as terpineol, butyl carbitol, butyl carbitol acetate can be used . These compounding ratios are adjusted according to the viscosity of the thick film resistance paste calculated
  • a solvent having a high boiling point can be added in order to delay the drying of the thick film resistance paste.
  • the content of the organic vehicle is not particularly limited, it is generally 30 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the inorganic raw material powder in order to obtain a suitable viscosity in the compounding ratio with the various components described above. It is.
  • the thick film resistive paste of the present invention can be obtained by dispersing a composition for a thick film resistor comprising silver powder, ruthenium oxide based conductive powder and glass frit in an organic vehicle. .
  • the method of producing thick film resistor pastes of the present invention can be used with planet mills, bead mills, etc. There is no need to limit the manufacturing method.
  • the silver powder, the ruthenium oxide-based conductive powder, and the glass frit used in the present invention may be previously mixed in a ball mill or a grinder and then dispersed in an organic vehicle.
  • the inorganic raw material powder may cause aggregation of the inorganic raw material powders to form a coarse secondary particle powder, and therefore, such a coarse powder may be crushed and then the resin component is dissolved in a solvent in an organic vehicle. It is desirable to disperse in In general, when the particle size of the inorganic raw material powder is reduced, the aggregation becomes strong and the secondary particles are easily formed.
  • the thick film resistor paste according to the present invention examples of the thick film resistor paste according to the present invention, the composition for the thick film resistor which is the material thereof, and the thick film resistor formed using the thick film resistor paste will be described.
  • the present invention is not limited by these examples.
  • the film thickness of the thick film resistors in Examples and Comparative Examples described later was measured using a stylus type thickness roughness meter.
  • the resistance value of the thick film resistor was measured by a digital multimeter.
  • pulse trimming of the thick film resistors in the example and the comparative example was performed by charging a 200 pF-0 ⁇ unit with a voltage of 2 to 5 kV and then discharging the thick film resistors.
  • the resistance value before discharge was set to R0
  • the resistance value after discharge was set to R1
  • the change rate of the resistance value after discharge was computed by the following formula
  • Change rate of resistance value by pulse trimming (R1-R0) / R0 x 100 ... (1)
  • the rate of change of the resistance value calculated by the above equation (1) is used as the amount of change of the resistance value that can be adjusted using the adjustment method using pulse trimming.
  • each material was mixed by the composition shown in Table 1, and a composition for a thick film resistor and a thick film resistor paste were produced.
  • the compounding amounts of the materials were adjusted such that the numerical value range of the area resistance value of the formed thick film resistors became wide.
  • the area resistance values of the formed thick film resistors were 1 k ⁇ , 10 k ⁇ , 110 k ⁇ , and 800 k ⁇ , respectively.
  • the compounding quantity of the organic vehicle became the quantity of about 35 mass%.
  • a three roll mill was used to prepare a thick film resistor paste.
  • These thick film resistor pastes were printed, dried and fired on an alumina substrate having a purity of 96% by mass to form and evaluate thick film resistors.
  • the prepared thick film resistor paste is printed on an electrode of 1% by mass of Pd and 99% by mass of Ag previously formed by firing on an alumina substrate and dried at 150 ° C. for 5 minutes,
  • the thick film resistor was formed by firing using a belt furnace configured to perform heat treatment for 30 minutes in total for a peak temperature of 850 ° C. ⁇ 9 minutes.
  • the thick film resistor was printed so that the size was 1 mm in the width of the resistor, 1 mm in the length of the resistor, and 7 ⁇ m in thickness, and the final film thickness was confirmed after firing.
  • Various evaluation results are shown in Table 1.
  • the negative value of the change rate (%) of resistance value shown in Table 1 has shown the change rate of the resistance value which changes to a fall direction.
  • the absolute value of the change rate of the resistance value changing in the decreasing direction is defined as the decrease rate of the resistance value.
  • compositions for thick film resistors, thick film resistor pastes and thick film resistors of Comparative Examples 5 and 6 are the same as the compositions for thick film resistors of Comparative Examples 1 to 4, inorganic materials for thick film resistor paste and thick film resistors.
  • the ruthenium oxide powder was changed to a powder having an average particle diameter of 30 nm, it was manufactured in substantially the same manner as Comparative Examples 1 to 4.
  • the compositions for thick film resistors, thick film resistor pastes and thick film resistors of Comparative Examples 7 and 8 are the compositions for thick film resistors of Comparative Examples 1 to 4, thick film resistor paste and thick film resistors.
  • Examples 1 to 4 The compositions for thick film resistors, thick film resistor pastes and thick film resistors of Examples 1 to 4 are the same as the compositions for thick film resistors of Comparative Examples 1 to 4, inorganic materials for thick film resistor paste and thick film resistors.
  • silver powder having an average particle diameter of 3 ⁇ m was added to the conductive powder, and the other components were manufactured in substantially the same manner as Comparative Examples 1 to 4.
  • the compounding quantity of each material and various evaluation results are shown in Table 3.
  • the rate of change (%) in resistance shown in Table 3 also indicates the rate of change in resistance that changes in the decreasing direction.
  • compositions for thick film resistors, thick film resistor pastes and thick film resistors of Examples 5 and 6 are the same as the compositions for thick film resistors of Examples 1 to 4, inorganic materials for thick film resistor paste and thick film resistors.
  • manufacture was substantially the same as in Examples 1 to 4 except that the ruthenium oxide powder was changed to a powder having an average particle diameter of 30 nm.
  • the composition for a thick film resistor, the thick film resistor paste and the thick film resistor of Example 7 are the same as those of the compositions for a thick film resistor, the thick film resistor paste and the thick film resistor of Examples 1 to 4.
  • compositions for thick film resistors, thick film resistor pastes and thick film resistors of Examples 8 and 9 are the compositions for thick film resistors of Examples 1 to 4, thick film resistor paste and thick film resistors.
  • inorganic components in Example 1 substantially the same as Examples 1 to 4 except that silver powder having an average particle diameter of 0.1 ⁇ m in Example 8 and an average particle diameter of 5.0 ⁇ m in Example 9 was added to the conductive powder.
  • composition for thick film resistor, thick film resistor paste and thick film resistor of Example 10 are the same as the composition for thick film resistor, thick film resistor paste and thick film resistor of Examples 1 to 4.
  • Example 1 to Example 1 except that silver powder having an average particle diameter of 3 ⁇ m was contained in the conductive powder at a value close to the lower limit 10% by mass of the content range of silver powder in the thick film resistor paste of the present invention Manufactured substantially as in 4.
  • the composition for a thick film resistor, the thick film resistor paste and the thick film resistor of Example 11 are the same as the compositions for the thick film resistor, the thick film resistor paste and the thick film resistor of Examples 1 to 4, respectively.
  • the same preparation as in Examples 1 to 4 was carried out except that ruthenium oxide powder was contained at a value close to the upper limit value of 30% by mass of the content range of ruthenium oxide powder in the thick film resistor paste of the present invention. .
  • the blending amounts of the respective materials and the various evaluation results are shown in Table 4.
  • the change rate (%) of the resistance value shown in Table 4 also indicates the change rate of the resistance value changing in the decreasing direction.
  • the area resistance value of the formed thick film resistor is respectively 0.07 k ⁇ , 15 k ⁇ , 0.08 k ⁇ , 0.08 k ⁇ , 20 k ⁇ , It became 0.09k ⁇ and 0.08k ⁇ .
  • the blending amount of the organic vehicle is about 30 to 31 mass% in Examples 5, 6, 7, 9 and 34 in Example 8. The amount was about mass%, and in Example 10, about 37 mass%. Further, in Example 11, the ruthenium oxide powder is contained at a value close to the upper limit 30 mass% of the content range of the ruthenium oxide powder in the thick film resistor paste of the present invention, and a considerable amount of silver powder is also contained. The blending amount of the vehicle was about 22% by mass, which was the smallest among the examples and the comparative examples.
  • the conductive powder is a mixed powder of ruthenium oxide and lead ruthenate.
  • the reduction rate of the resistance value as the amount of change of the resistance value due to the voltage load of the pulse trimming by setting the ruthenium oxide type conductive material powder comprising the above and the silver powder having an average particle diameter in the range of 0.1 ⁇ m to 5.0 ⁇ m.
  • silver powder is not contained in the conductive substance powder in Comparative Examples 1 to 6 of Tables 1 and 2 and silver powder is contained in the conductive substance powder, the average particle diameter of the silver powder is 0.1 ⁇ m to 5.0 ⁇ m.
  • the thick film resistor composition of the present invention and the thick film resistor manufactured using the thick film resistor paste the conventional thick film resistor not containing silver powder or the one containing silver powder Of the resistance value as the amount of change of the resistance value that can be adjusted using the adjustment method by pulse trimming as compared with the thick film resistor in which the average particle diameter of the silver powder is out of the range of 0.1 ⁇ m to 5.0 ⁇ m.
  • the rate of decline can be increased.
  • composition for a thick film resistor, the thick film resistor paste, and the thick film resistor according to the present invention have a decrease rate of the resistance value as a change amount of the resistance value which can be adjusted using an adjustment method by pulse trimming at the time of forming the resistor.
  • a decrease rate of the resistance value as a change amount of the resistance value which can be adjusted using an adjustment method by pulse trimming at the time of forming the resistor.

Abstract

[Problem] To provide: a composition for a thick film resistor having a high rate of decrease in resistance value as an amount of change in a resistance value that can be adjusted by an adjustment method using pulse trimming when forming a resistor; a thick film resistance paste; and a thick film resistor. [Solution] This composition for a thick film resistor contains ruthenium oxide-based conductive powder comprising mixed powder of ruthenium oxide and lead-ruthenium, and glass frit, and further contains silver powder of 16-33 mass%, wherein, when a thick film resistor is formed by sintering a thick film resistance paste to which an organic vehicle is added, the rate of decrease in resistance value of the thick film resistor, which can be adjusted by an adjustment method using pulse trimming, is set to be larger than 5%.

Description

厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体Composition for thick film resistor, thick film resistor paste and thick film resistor
　本発明は、厚膜チップ抵抗器やハイブリッドＩＣ、または、サーマルヘッドなどの抵抗体を形成するために使用される厚膜抵抗ペーストと、その材料である厚膜抵抗体用組成物、及び厚膜抵抗ペーストを用いて形成した厚膜抵抗体に関するものである。 The present invention relates to a thick film resistor paste used for forming a resistor such as a thick film chip resistor, a hybrid IC, or a thermal head, a composition for a thick film resistor which is the material, and a thick film. The present invention relates to a thick film resistor formed using a resistor paste.
　一般にチップ抵抗器、ハイブリッドＩＣ、または、サーマルヘッドなどに用いられる抵抗体は、セラミック基板に厚膜抵抗ペーストを印刷した後、焼成することによって形成される。このような厚膜抵抗ペーストを用いて形成される抵抗体は、スパッタなどの方法により形成される抵抗体に比べて膜厚が厚いため、一般に厚膜抵抗体と称される。厚膜抵抗体には、導電粒子として酸化ルテニウムを代表とする酸化ルテニウム系導電物粉末とガラス粉末を主な成分とした組成物が広く用いられている。
　酸化ルテニウム系導電物粉末とガラス粉末が厚膜抵抗体用組成物の主成分として広く用いられている理由は、空気中で焼成することができ、抵抗温度係数（ＴＣＲ）を０に近づけることが可能であることに加え、幅広い領域で各種抵抗値を有する抵抗体を形成することが可能であることなどが挙げられる。
　酸化ルテニウム系導電物粉末とガラス粉末からなる厚膜抵抗体用組成物では、酸化ルテニウム系導電物粉末とガラス粉末の配合比を変えることによって、各種抵抗値を有する抵抗体を形成することができる。導電粒子である酸化ルテニウム系導電物粉末の配合比を多くすると抵抗値が下がり、酸化ルテニウム系導電物粉末の配合比を少なくすると抵抗値が上がる。このことを利用して、厚膜抵抗体では、厚膜抵抗体用組成物における酸化ルテニウム系導電物粉末とガラス粉末の配合比を調整することにより所望する抵抗値を得ることができる。 In general, a resistor used for a chip resistor, a hybrid IC, a thermal head or the like is formed by printing a thick film resistor paste on a ceramic substrate and then firing it. A resistor formed using such a thick film resistor paste is generally referred to as a thick film resistor because the film thickness is thicker than a resistor formed by a method such as sputtering. As a thick film resistor, a composition having a ruthenium oxide-based conductive powder typified by ruthenium oxide as a conductive particle and a glass powder as main components is widely used.
The reason why ruthenium oxide-based conductive powder and glass powder are widely used as the main components of the composition for thick film resistors is that they can be fired in air, and the temperature coefficient of resistance (TCR) can be close to 0 Besides being possible, it is possible to form a resistor having various resistance values in a wide range.
In a composition for a thick film resistor comprising a ruthenium oxide based conductive powder and a glass powder, resistors having various resistance values can be formed by changing the compounding ratio of the ruthenium oxide based conductive powder and the glass powder. . When the compounding ratio of the ruthenium oxide-based conductive material powder which is conductive particles is increased, the resistance value decreases, and when the compounding ratio of the ruthenium oxide-based conductive material powder is decreased, the resistance value increases. Utilizing this, in the thick film resistor, a desired resistance value can be obtained by adjusting the compounding ratio of the ruthenium oxide based conductive material powder and the glass powder in the composition for a thick film resistor.
　酸化ルテニウム系導電物として最も一般的なものは、ルチル型の結晶構造を有する酸化ルテニウム（ＲｕＯ２）であり、後述する酸化ルテニウム系導電物の種類の中では比抵抗が最も低い。酸化ルテニウム（ＲｕＯ２）粉末とガラス粉末の組み合わせでは、一般に１０－２Ω・ｃｍ～１０４Ω・ｃｍ（１０－４Ω・ｍ～１０２Ω・ｍ）の領域の抵抗体が形成できる。
　ルチル型の結晶構造を有する酸化ルテニウム（ＲｕＯ２）の他の酸化ルテニウム系導電物としては、パイロクロア型の結晶構造を有するルテニウム酸鉛、ルテニウム酸ビスマス、ペロブスカイト型結晶構造を有するルテニウム酸カルシウム、ルテニウム酸ストロンチウム、ルテニウム酸バリウム、ルテニウム酸ランタン等があり、これらはいずれも金属的な導電性を示す酸化物である。
　このような酸化ルテニウム系導電物として、例えば、ルチル型の結晶構造を有する酸化ルテニウム（ＲｕＯ２）は、次の特許文献１に記載のように、不定形酸化ルテニウム化合物を焙焼して得たＲｕＯ２粒子に、ＫＯＨ及びＮａＯＨの少なくとも一方を被覆させ、再び焙焼した後、水洗、乾燥するなどの方法で製造することができる。 The most common ruthenium oxide-based conductive material is ruthenium oxide (RuO 2 ) having a rutile type crystal structure, and among the types of ruthenium oxide-based conductive materials described later, the specific resistance is the lowest. A combination of ruthenium oxide (RuO 2 ) powder and glass powder can generally form a resistor of 10 −2 Ω · cm to 10 4 Ω · cm (10 −4 Ω · m to 10 2 Ω · m).
Other ruthenium oxide-based conductors of ruthenium oxide (RuO 2 ) having a rutile crystal structure include lead ruthenate having a pyrochlore crystal structure, bismuth ruthenate, calcium ruthenate having a perovskite crystal structure, and ruthenium Strontium acid, barium ruthenate, lanthanum ruthenate and the like, all of which are oxides exhibiting metallic conductivity.
As such a ruthenium oxide based conductive material, for example, ruthenium oxide (RuO 2 ) having a rutile type crystal structure is obtained by roasting an amorphous ruthenium oxide compound as described in the following Patent Document 1 The RuO 2 particles can be coated with at least one of KOH and NaOH, roasted again, and then manufactured by a method such as washing with water, drying and the like.
　ガラスフリットとしては、ホウケイ酸鉛ガラス（ＰｂＯ－ＳｉＯ２－Ｂ２Ｏ３）やアルミナホウケイ酸鉛ガラス（ＰｂＯ－ＳｉＯ２－Ｂ２Ｏ３－Ａｌ２Ｏ３）等の鉛を含有するガラスや、ホウケイ酸ガラス、アルミナホウケイ酸ガラス、ホウケイ酸アルカリ土類ガラス、ホウケイ酸アルカリガラス、ホウケイ酸亜鉛ガラス、ホウケイ酸ビスマスガラス等の鉛を含有しないガラスが広く用いられている。 Glass frits include lead-containing glasses such as lead borosilicate glass (PbO-SiO 2 -B 2 O 3 ) and alumina lead borosilicate glass (PbO-SiO 2 -B 2 O 3 -Al 2 O 3 ); Lead-free glasses such as borosilicate glass, alumina borosilicate glass, alkaline earth borosilicate glass, alkali borosilicate glass, zinc borosilicate glass and bismuth borosilicate glass are widely used.
　厚膜抵抗ペーストは、厚膜抵抗体用組成物に有機ビヒクルを加えたものが基本構成となる。有機ビヒクルとしては、エチルセルロース、ブチラール、アクリル等の樹脂を、ターピネオール、ブチルカルビトールアセテート等の溶剤に溶解したものが広く用いられている。
　その他に、厚膜抵抗体の電気的特性などを調整するために、種々の添加剤、または、分散剤、可塑剤などが適宜添加される。
　また、厚膜抵抗ペーストは、上述した各種材料をロールミルなどの市販の装置を用いて、粉砕混合することにより製造される。 The thick film resistor paste is basically composed of a composition for a thick film resistor and an organic vehicle added thereto. As the organic vehicle, those obtained by dissolving a resin such as ethyl cellulose, butyral or acrylic in a solvent such as terpineol or butyl carbitol acetate are widely used.
In addition, various additives, dispersants, plasticizers and the like are appropriately added in order to adjust the electrical characteristics and the like of the thick film resistor.
In addition, the thick film resistor paste is manufactured by grinding and mixing the various materials described above using a commercially available device such as a roll mill.
　厚膜抵抗体は、アルミナセラミック基板やグレーズ層付きアルミナセラミック基板などの絶縁基板上に、Ａｌ、Ａｕ、Ａｇ等により予め形成されている電極間を、スクリーン印刷機やインクジェットなどの市販の塗布機を用いて、製造された厚膜抵抗ペーストを印刷し、その後、乾燥・焼成することで成膜して得ることができる。この段階では、成膜した厚膜抵抗体は、抵抗値のばらつきが大きい。このため、厚膜抵抗体に対し、所望の抵抗値に合わせこむための抵抗値の調整（トリミング）が行われる。 A thick film resistor is a commercially available coating machine such as a screen printer or an ink jet between electrodes which are previously formed of Al, Au, Ag or the like on an insulating substrate such as an alumina ceramic substrate or an alumina ceramic substrate with a glaze layer. The obtained thick film resistor paste is printed using the following method, and then dried and fired to form a film. At this stage, the deposited thick film resistor has a large variation in resistance value. Therefore, adjustment (trimming) of the resistance value is performed on the thick film resistor in order to adjust it to a desired resistance value.
　抵抗値の調整手法としては、レーザートリミングが最も広く採用されている。レーザートリミングとは、ＣＯ２等のレーザー光を厚膜抵抗体の一部に直接照射し、その熱により厚膜抵抗体の一部を溶解・気化させて厚膜抵抗体の一部を消失させ、厚膜抵抗体の一部を消失させることにより導電経路を狭くして抵抗値を上げて調整する方法である。
　しかし、レーザートリミングは、上述のように厚膜抵抗体の一部を溶解・気化させることによって、局所的に導電経路を狭くして抵抗体の抵抗値を調整する方法であるため、抵抗体内部に導電経路の狭い部分と広い部分が形成され電流密度の差が生じてしまう。局所的に生じた抵抗値の高い部分は、他の抵抗値の低い部分に比べて発熱量も高くなるため、抵抗体内部の発熱状態に差を生じてしまう。そのため、発熱体として利用するプリントヘッドやサーマルヘッドに、レーザートリミングした厚膜抵抗体を用いると、不均一な発熱分布になってしまう場合があり好ましくない。このため、発熱体として利用するプリントヘッドやサーマルヘッドに用いる厚膜抵抗体には、レーザートリミングによる抵抗値の調整は適さない。 Laser trimming is most widely adopted as a method of adjusting the resistance value. With laser trimming, laser light such as CO 2 is directly irradiated to a part of the thick film resistor, and the heat dissolves and vaporizes a part of the thick film resistor to lose part of the thick film resistor. This is a method of adjusting by narrowing the conductive path by raising a part of the thick film resistor and raising the resistance value.
However, since the laser trimming is a method of locally narrowing the conductive path and adjusting the resistance value of the resistor by melting and evaporating a part of the thick film resistor as described above, the inside of the resistor can be obtained. At the same time, a narrow portion and a wide portion of the conductive path are formed, resulting in a difference in current density. The locally generated high-resistance portion has a higher calorific value as compared to other low-resistance portions, which causes a difference in the heat generation state inside the resistor. Therefore, it is not preferable to use a thick film resistor which has been subjected to laser trimming for a print head or a thermal head used as a heating element, because the heat generation distribution may be uneven. For this reason, adjustment of the resistance value by laser trimming is not suitable for a thick film resistor used for a print head or a thermal head used as a heating element.
　このようなレーザートリミングによる厚膜抵抗体の抵抗値の調整における問題を解決しうる他の抵抗値の調整手法として、電気的負荷を厚膜抵抗体に加えることにより抵抗値の調整を行うパルストリミングと呼ばれる手法がある。なお、ここでの電気的負荷とは、電圧、電流により与える負荷のことを指す。パルストリミングは、厚膜抵抗体の電極間に製品使用時よりも高い電圧を印加することにより抵抗値を変動させて調整する手法で、電圧を印加した際にその電圧の大きさに応じて抵抗値が変化するという厚膜抵抗体の性質を利用した手法であり、抵抗値は低くなる場合が多い。パルストリミングは、特に、近年の微細化、高精細化の進んだ微細電子部品に関して非常に有効な厚膜抵抗体の抵抗値の調整手法である。
　パルストリミングを用いた厚膜抵抗体の抵抗値の調整に関する技術は、例えば、次の特許文献２～４に開示されている。 As another adjustment method of the resistance value which can solve the problem in adjustment of the resistance value of the thick film resistor by such laser trimming, pulse trimming which adjusts the resistance value by applying an electric load to the thick film resistor There is a method called In addition, the electrical load here refers to the load given by voltage and current. Pulse trimming is a method in which the resistance value is varied and adjusted by applying a higher voltage than when using the product between the electrodes of a thick film resistor, and when a voltage is applied, the resistance is adjusted according to the magnitude of the voltage. It is a method that utilizes the property of a thick film resistor whose value changes, and the resistance value is often low. The pulse trimming is a method of adjusting the resistance value of the thick film resistor which is very effective particularly for the recent miniaturization and high definition of fine electronic components.
Techniques relating to adjustment of the resistance value of a thick film resistor using pulse trimming are disclosed, for example, in the following Patent Documents 2 to 4.
　例えば、特許文献２には、一度電圧パルストリミングを行った後、一定温度、一定時間加熱し、再度電圧パルストリミングを行うサーマルヘッドの製造方法が開示されている。 For example, Patent Document 2 discloses a method of manufacturing a thermal head in which voltage pulse trimming is performed once, heating is performed at a constant temperature for a predetermined time, and voltage pulse trimming is performed again.
　また、例えば、特許文献３には、電圧パルストリミングを行った後、抵抗値を測定したプローブを介して、必要に応じて電圧パルスを印加してサーマルヘッドの抵抗値を微調整する方法が開示されている。 Further, for example, Patent Document 3 discloses a method of finely adjusting the resistance value of the thermal head by applying a voltage pulse as necessary through a probe whose resistance value has been measured after performing voltage pulse trimming. It is done.
　また、例えば、特許文献４には、一対の電極に対して第１の方向に電圧を印加した後、第１の方向とは反対の第２の方向に電圧を印加する抵抗値の調整方法が開示されている。 For example, Patent Document 4 discloses a method of adjusting a resistance value in which a voltage is applied in a first direction to a pair of electrodes, and then a voltage is applied in a second direction opposite to the first direction. It is disclosed.
　このようなパルストリミングによる厚膜抵抗体の抵抗値の調整方法は、レーザートリミングと異なり、抵抗体の形状を変化させることが無いため、抵抗体内で均一的な抵抗値分布を持った厚膜抵抗体を得ることができるため、プリントヘッドやサーマルヘッド用の厚膜抵抗体の抵抗値の調整に適した手法である。
　具体的には、あらかじめ抵抗値調整対象の厚膜抵抗体の印加電圧と抵抗値の変化量との関係を確認しておき、抵抗値の調整時に、抵抗値の調整を行う厚膜抵抗体の抵抗値を測定し、測定した厚膜抵抗体の抵抗値から所望の抵抗値に調整するために必要な抵抗値の変化量を求め、求めた抵抗値の変化量に応じて印加する電圧値を選択し、厚膜抵抗体に印加することで所望の抵抗値を得る。 Unlike the laser trimming, the method of adjusting the resistance value of the thick film resistor by such pulse trimming does not change the shape of the resistor, so that the thick film resistance having a uniform resistance value distribution in the resistor body This method is suitable for adjusting the resistance value of a thick film resistor for a print head or a thermal head because it can obtain a body.
Specifically, the relationship between the applied voltage of the thick film resistor subject to resistance value adjustment and the change amount of the resistance value is confirmed in advance, and the adjustment of the resistance value is performed when adjusting the resistance value. The resistance value is measured, and from the measured resistance value of the thick film resistor, the change amount of the resistance value required to adjust to the desired resistance value is determined, and the voltage value applied according to the determined change amount of the resistance value The desired resistance value is obtained by selecting and applying to the thick film resistor.
　従来、特許文献２～４に開示のように、各種パルストリミングの方法が開発されてきたが、調整可能な抵抗値の変化量は厚膜抵抗体、厚膜抵抗ペーストの組成に大きく依存しているにもかかわらず、パルストリミングに適した厚膜抵抗ペースト及び、厚膜抵抗体用組成物についての開発はあまり行われていない。即ち、従来、パルストリミングの方法を工夫することにより調整可能な抵抗値の変化量を増やしてはいるが、電圧を繰り返し印加することにより得られる抵抗値の変化量は、電圧の印加回数が増えるに従い減少してしまうため、パルストリミングの方法により調整可能な抵抗値の変化量に限界が生じてしまうのは避けられない。 Conventionally, as disclosed in Patent Documents 2 to 4, various pulse trimming methods have been developed, but the amount of change in adjustable resistance value largely depends on the composition of the thick film resistor and the thick film resistor paste. Nevertheless, there has not been much development of thick film resistor pastes suitable for pulse trimming and compositions for thick film resistors. That is, although the amount of change in the adjustable resistance value is conventionally increased by devising the method of pulse trimming, the amount of change in resistance value obtained by repeatedly applying the voltage increases the number of times of voltage application. Since it decreases in accordance with the above, it is inevitable that the method of pulse trimming causes a limit to the amount of change in the adjustable resistance value.
特開平８－２６８７２２号公報JP-A-8-268722 特開平０２－１３０１５６号公報JP 02-130156 A 特開平０５－３０５７２２号公報Japanese Patent Application Laid-Open No. 05-305722 特開２００４－２４７３９８号公報Japanese Patent Application Laid-Open No. 2004-247398
　上述のように、パルストリミングによる調整手法を用いて抵抗値調整を行う厚膜抵抗体において、１回のパルストリミングによって調整可能な抵抗値の変化量は、用いる厚膜抵抗体、厚膜抵抗ペーストの組成による影響が最も大きい。パルストリミングによる調整手法を用いた抵抗値の調整は、レーザートリミングによる調整手法を用いた抵抗値の調整のように抵抗値を上げて調整するのとは異なり、抵抗値を下げて調整する場合が多いため、厚膜抵抗体は所望の抵抗値よりも高くなるように形成しておく必要がある。そして、形成する厚膜抵抗体の抵抗値のばらつきを考慮し、所望の抵抗値に比べてかなり高めの抵抗値になるように設計して厚膜抵抗体を形成するのが一般的である。そのため、形成した厚膜抵抗体の抵抗値をパルストリミングにより所望の抵抗値に下げるためには、比較的高い電圧を印加する必要がある。しかしながら、他の電気素子への影響などから、回路の構成上高過ぎる電圧は印加できない場合もあり、１回の抵抗値の調整量が限定されてしまう場合が多く、所望の抵抗値に下げるまでに、パルストリミングを複数回行う必要が生じる場合がある。しかるに、パルストリミングは、回数を重ねるごとに抵抗値の変化量が減少してしまう。また、従来の厚膜抵抗体は、電圧印加時における調整可能な抵抗値の変化量としての抵抗値の低下率が小さい。このため、従来の厚膜抵抗体を用いてパルストリミングを複数回行う際、著しく印加回数が多くなってしまう場合があり、レーザートリミングなどに比べて生産性が低くなってしまう、さらには、所望の抵抗値までの下げ幅が大き過ぎる場合には所望の抵抗値にまで下げることが困難な場合が生じてしまう虞がある。従来の厚膜抵抗体を用いてパルストリミングで抵抗値を調整する場合において、所望の抵抗値にまで確実に下げることができるようにするには、トリミング前の抵抗値を低めの抵抗値に設計して厚膜抵抗体を形成することが考えられるが、最終目標の所望の抵抗値に近い、低めの抵抗値に設計して厚膜抵抗体を形成すると、所望の抵抗値よりも低い抵抗値の厚膜抵抗体が形成されてしまう割合が増加し、歩留まりが悪くなってしまう虞がある。 As described above, in a thick film resistor in which the resistance value is adjusted using the adjustment method by pulse trimming, the change amount of the resistance value adjustable by one pulse trimming is the thick film resistor used, the thick film resistor paste The influence of the composition of the The adjustment of the resistance value using the adjustment method by pulse trimming is different from the adjustment by raising the resistance value like the adjustment of the resistance value using the adjustment method by laser trimming, but the adjustment may be performed by lowering the resistance value. Since there are many, it is necessary to form a thick film resistor so as to be higher than a desired resistance value. Then, in consideration of the dispersion of the resistance value of the thick film resistor to be formed, it is general to form the thick film resistor by designing so that the resistance value becomes considerably higher than the desired resistance value. Therefore, in order to reduce the resistance value of the formed thick film resistor to a desired resistance value by pulse trimming, it is necessary to apply a relatively high voltage. However, due to the influence on other electrical elements, etc., a voltage that is too high may not be applied due to the circuit configuration, and in many cases the amount of adjustment of the resistance value is limited once, until the desired resistance value is reduced. In some cases, it may be necessary to perform pulse trimming multiple times. However, in the pulse trimming, the amount of change in resistance decreases as the number of repetitions increases. Further, in the conventional thick film resistor, the decrease rate of the resistance value as the change amount of the adjustable resistance value at the time of voltage application is small. Therefore, when pulse trimming is performed multiple times using a conventional thick film resistor, the number of times of application may be significantly increased, and the productivity is lower than that of laser trimming, etc. If the reduction width to the resistance value is too large, it may be difficult to lower the resistance value to a desired resistance value. In the case of adjusting the resistance value by pulse trimming using a conventional thick film resistor, the resistance value before trimming is designed to be a lower resistance value so that the desired resistance value can be reliably lowered. It is conceivable to form a thick film resistor, but if the thick film resistor is designed to have a lower resistance value close to the desired resistance value of the final target, the resistance value is lower than the desired resistance value. The rate at which the thick film resistor is formed is increased, and the yield may be deteriorated.
　本発明は、上記従来の課題を鑑みてなされたものであり、抵抗体形成時におけるパルストリミングによる調整手法を用いて調整可能な抵抗値の変化量としての抵抗値の低下率が大きな厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体を提供することを目的とする。 The present invention has been made in view of the above-mentioned conventional problems, and a thick film resistance having a large reduction rate of resistance value as a change amount of resistance value adjustable using an adjustment method by pulse trimming at the time of forming a resistor. It is an object of the present invention to provide a body composition, a thick film resistor paste and a thick film resistor.
　上記課題を解決するため、本発明者は鋭意研究を重ねた結果、厚膜抵抗体用組成物を、酸化ルテニウムとルテニウム酸鉛の混合粉末からなる酸化ルテニウム系導電物粉末に加えて、１６質量％以上３３質量％以下の銀粉末を含有させた構成とすることにより、この厚膜抵抗体用組成物を用いて製造した厚膜抵抗体において、パルストリミングによる調整手法を用いて調整可能な抵抗値の変化量である抵抗値の低下率を増大させることができることを見出し、本発明を完成するに至った。
　本発明による厚膜抵抗体用組成物は、酸化ルテニウムとルテニウム酸鉛の混合粉末からなる酸化ルテニウム系導電物粉末と、ガラスフリットを含有する厚膜抵抗体用組成物において、１６質量％以上３３質量％以下の銀粉末を更に含有し、有機ビヒクルを加えた厚膜抵抗ペーストを焼結して厚膜抵抗体を形成したときの、該厚膜抵抗体におけるパルストリミングによる調整手法を用いて調整可能な抵抗値の低下率が５％より大きくなるようにしたことを特徴としている。 In order to solve the above problems, as a result of intensive studies, the present inventor added 16 wt% of a composition for a thick film resistor to a ruthenium oxide based conductive powder comprising a mixed powder of ruthenium oxide and lead ruthenate. In the thick film resistor manufactured using the composition for a thick film resistor, the resistance that can be adjusted using the adjustment method by pulse trimming by using a composition containing silver powder of at least 33% by mass. The inventors have found that the rate of decrease in resistance value, which is the amount of change in value, can be increased, and the present invention has been completed.
The composition for a thick film resistor according to the present invention comprises 16 mass% or more of a composition for a thick film resistor containing a ruthenium oxide conductive powder comprising a mixed powder of ruthenium oxide and lead ruthenate and a glass frit. Adjustment is carried out using a pulse trimming method in a thick film resistor when a thick film resistor is formed by sintering a thick film resistor paste further containing silver powder of not more than% by mass and adding an organic vehicle It is characterized in that the reduction rate of the possible resistance value is made larger than 5%.
　また、本発明の厚膜抵抗体用組成物においては、前記銀粉末の平均粒径が０．１μｍ以上５μｍ以下であり、前記酸化ルテニウム系導電物粉末の平均粒径が１ｎｍ以上５００ｎｍ以下であり、前記ガラスフリットの平均粒径が０．１μｍ以上５μｍ以下であるのが好ましい。 In the composition for a thick film resistor according to the present invention, the average particle diameter of the silver powder is 0.1 μm to 5 μm, and the average particle diameter of the ruthenium oxide-based conductive powder is 1 nm to 500 nm. The average particle diameter of the glass frit is preferably 0.1 μm to 5 μm.
　また、本発明の厚膜抵抗体用組成物においては、前記酸化ルテニウム粉末の平均粒径が７ｎｍ以上３０ｎｍ以下であるのが好ましい。 Further, in the composition for a thick film resistor according to the present invention, the average particle diameter of the ruthenium oxide powder is preferably 7 nm or more and 30 nm or less.
　また、本発明の厚膜抵抗体用組成物においては、前記ルテニウム酸鉛粉末の平均粒径が５ｎｍ以上５０ｎｍ以下であるのが好ましい。 Further, in the composition for a thick film resistor according to the present invention, the average particle diameter of the lead ruthenate powder is preferably 5 nm or more and 50 nm or less.
　また、本発明による厚膜抵抗ペーストは、上記本発明のいずれかの厚膜抵抗体用組成物に、更に有機ビヒクルを加えてなることを特徴としている。 The thick film resistor paste according to the present invention is characterized in that an organic vehicle is further added to the composition for a thick film resistor according to any of the above-mentioned present invention.
　また、本発明の厚膜抵抗ペーストにおいては、前記銀粉末を１０質量％以上２０質量％以下、前記酸化ルテニウム系導電物粉末を総量で５質量％以上３０質量％以下、前記ガラスフリットを１５質量％以上７０質量％以下含有し、残部が前記有機ビヒクルからなるのが好ましい。 In the thick film resistor paste of the present invention, 10% by mass or more and 20% by mass or less of the silver powder, 5% by mass or more and 30% by mass or less in total of the ruthenium oxide conductive powder, and 15% by mass of the glass frit It is preferable that the content is in the range of 70% by mass to 70% by mass, and the balance is made of the organic vehicle.
　また、本発明の厚膜抵抗ペーストにおいては、前記酸化ルテニウム系導電物粉末を総量で５質量％以上９．３質量％以下含有するのが好ましい。 Moreover, in the thick film resistance paste of this invention, it is preferable to contain 5 mass% or more and 9.3 mass% or less in total of the said ruthenium oxide type electrically conductive powder.
　また、本発明による厚膜抵抗体は、上記本発明のいずれかの厚膜抵抗ペーストの焼結体であることを特徴としている。 Furthermore, the thick film resistor according to the present invention is characterized in that it is a sintered body of any of the above-mentioned present invention thick film resistor pastes.
　また、本発明の厚膜抵抗体においては、パルストリミングによる調整手法を用いて調整可能な抵抗値の低下率が５％より大きいのが好ましい。 Further, in the thick film resistor of the present invention, it is preferable that the reduction rate of the resistance value that can be adjusted by using the adjustment method by pulse trimming be larger than 5%.
　本発明によれば、従来一般に広く用いられている銀粉末を含有しない厚膜抵抗ペーストを用いて形成した厚膜抵抗体に比べて、抵抗体形成時におけるパルストリミングによる調整手法を用いて調整可能な抵抗値の変化量としての抵抗値の低下率を増大させることができ、パルストリミングに要する回数、及び時間を短縮し、抵抗体の生産性を向上させることが可能な厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体が得られる。 According to the present invention, adjustment is possible using the adjustment method by pulse trimming at the time of forming a resistor, compared to a thick film resistor formed using a thick film resistor paste containing no silver powder, which is generally used widely in the prior art Composition of a thick film resistor capable of increasing the reduction rate of the resistance value as the change amount of the resistance value, shortening the number of times and time required for pulse trimming, and improving the productivity of the resistor , A thick film resistor paste and a thick film resistor are obtained.
　以下、本発明の厚膜抵抗ペーストと、その材料である厚膜抵抗体用組成物、及び、前記厚膜抵抗ペーストを用いて形成した厚膜抵抗体について詳細に説明する。 Hereinafter, the thick film resistor paste of the present invention, the composition for a thick film resistor which is the material thereof, and the thick film resistor formed by using the thick film resistor paste will be described in detail.
１．銀粉末
　銀は、本発明におけるパルストリミングによる調整手法を用いて調整可能な抵抗値の変化量（抵抗値の低下率）を増大させるために必須の元素であり、本発明では、平均粒径が０．１μｍ以上５μｍ以下の銀粉末を用いる。銀粉末の平均粒径が０．１μｍ未満であると、製造コストが高くなる上、ハンドリング性が低下し、二次凝集による粗大化によって分散性の悪化が起こるため好ましくない。平均粒径が５μｍより大きくなる場合も、分散性の悪化が起こるため好ましくない。本発明に用いる銀粉末は、例えば硝酸銀をアルカリで一旦酸化銀の沈殿とし、これをポリビニルピロリドンなどの分散剤の存在下でテトラヒドロホウ酸ナトリウム、ヒドラジン、ホルマリン等の還元剤を用いて、還元することによって得ることができる。
　なお、本発明において平均粒径とは、レーザー回折散乱法で求められる体積基準平均粒径を意味し、レーザー回折散乱式粒度分布測定装置による５０％累計粒度によって得られる値である。この平均粒径の定義は、後述する酸化ルテニウム系導電物粉末やガラスフリットにおいても適用される。
　また、銀粉末の含有量は、パルストリミング量に応じて適宜選定すれば良いが、厚膜抵抗体用組成物１００質量％に対し、１６質量％以上３３質量％以下とする。銀粉末を含有させることによりパルストリミング時に調整可能な抵抗値量を増大させることができるが、抵抗値の変化量としての抵抗値の低下率を５％より大きくし効率的に抵抗値を変化させるために、銀粉末の含有量を、１６質量％以上とする。銀粉末を３３質量％より多く含有させてもそれ以上は変化率が大きく変わらないため、コスト的な面から３３質量％以下とするのが好ましい。なお、厚膜抵抗ペースト１００質量％に対する銀粉末の含有量は、１０質量％以上２０質量％以下とするのが好ましい。 1. Silver powder Silver is an essential element to increase the amount of change in resistance (the rate of decrease in resistance) that can be adjusted using the adjustment method by pulse trimming in the present invention, and in the present invention, the average particle diameter is A silver powder of 0.1 μm to 5 μm is used. If the average particle size of the silver powder is less than 0.1 μm, the production cost is increased, the handling property is lowered, and the dispersibility is deteriorated due to the coarsening due to the secondary aggregation, which is not preferable. Even when the average particle size is larger than 5 μm, it is not preferable because deterioration of dispersibility occurs. The silver powder to be used in the present invention is, for example, an alkali of silver nitrate once precipitated as a precipitate of silver oxide, which is reduced using a reducing agent such as sodium tetrahydroborate, hydrazine or formalin in the presence of a dispersing agent such as polyvinylpyrrolidone. Can be obtained by
In the present invention, the average particle size means a volume-based average particle size determined by a laser diffraction scattering method, and is a value obtained by 50% cumulative particle size by a laser diffraction scattering type particle size distribution measuring apparatus. The definition of the average particle diameter also applies to a ruthenium oxide based conductive material powder and a glass frit described later.
The content of the silver powder may be appropriately selected according to the amount of pulse trimming, but is 16 mass% or more and 33 mass% or less with respect to 100 mass% of the composition for a thick film resistor. By including silver powder, it is possible to increase the amount of resistance that can be adjusted at the time of pulse trimming, but the rate of decrease in resistance as a change in resistance is increased by more than 5% to efficiently change the resistance. Therefore, the content of silver powder is 16% by mass or more. Even if more than 33% by mass of silver powder is contained, the rate of change is not significantly changed, and therefore it is preferable to be 33% by mass or less from the viewpoint of cost. In addition, it is preferable to make content of the silver powder with respect to 100 mass% of thick film resistance pastes into 10 mass% or more and 20 mass% or less.
２．酸化ルテニウム系導電物粉末
　本発明では、厚膜抵抗体用の導電物粉末として、酸化ルテニウム系導電物粉末を用いる。酸化ルテニウム系導電物粉末には、ルチル型の結晶構造を有する酸化ルテニウム（ＲｕＯ２）と、パイロクロア型の結晶構造を有するルテニウム酸鉛（Ｐｂ２Ｒｕ２Ｏ６）の粉末を混合して用いる。
　酸化ルテニウム系導電物粉末の平均粒径は、１ｎｍ以上５００ｎｍ以下である。酸化ルテニウム系導電物粉末の平均粒径が１ｎｍ未満であると、取り扱いが非常に困難になる上、厚膜抵抗ペーストの粘度が非常に高くなり過ぎるため好ましくない。酸化ルテニウム系導電物粉末の平均粒径が５００ｎｍよりも大きいと、近年の微小化した電子部品に対し、形成される抵抗体の厚みが厚くなり過ぎる場合があるため好ましくない。ＲｕＯ２粉末は、例えば湿式で合成された水和したＲｕＯ２粉末を熱処理することによって得ることができる。その場合、ＲｕＯ２粉末の平均粒径は、７ｎｍ以上３０ｎｍ以下であるのが好ましい。Ｐｂ２Ｒｕ２Ｏ６粉末は、例えば湿式で合成されたＲｕ（ＯＨ）４粉末とＰｂＯ粉末を混合し、熱処理することによって得ることができる。Ｐｂ２Ｒｕ２Ｏ６粉末の平均粒径は、５ｎｍ以上５００ｎｍ以下であるのが好ましい。より好ましくは、Ｐｂ２Ｒｕ２Ｏ６粉末の平均粒径は、５ｎｍ以上５０ｎｍ以下であるのが良い。
　このような酸化ルテニウム系導電物粉末の含有量は、形成する抵抗値に応じて適宜選定すれば良いが、厚膜抵抗ペースト１００質量％に対し、総量で５質量％以上３０質量％以下とするのが好ましい。酸化ルテニウム系導電物粉末の含有により、抵抗体内の導電経路を形成させるが、酸化ルテニウム系導電物粉末の含有量が５質量％より少ないと抵抗値が上がり過ぎ、場合によっては電気が流れない場合があるため好ましくない。酸化ルテニウム系導電物粉末の含有量が３０質量％を超えると、導電経路が出来過ぎて十分な抵抗値が得られない場合があるため好ましくない。より好ましくは、酸化ルテニウム系導電物粉末の含有量は、厚膜抵抗ペースト１００質量％に対し、総量で５質量％以上９．３質量％以下とするのが良い。 2. Ruthenium Oxide Conductive Powder In the present invention, a ruthenium oxide conductive powder is used as a conductive powder for a thick film resistor. A powder of ruthenium oxide (RuO 2 ) having a rutile crystal structure and a powder of lead ruthenate (Pb 2 Ru 2 O 6 ) having a pyrochlore crystal structure are used as the ruthenium oxide conductive powder.
The average particle diameter of the ruthenium oxide based conductive material powder is 1 nm or more and 500 nm or less. If the average particle diameter of the ruthenium oxide based conductive material powder is less than 1 nm, handling becomes very difficult and the viscosity of the thick film resistive paste becomes too high, which is not preferable. If the average particle diameter of the ruthenium oxide based conductive material powder is larger than 500 nm, the thickness of the resistor to be formed may be too thick for the recent miniaturized electronic parts, which is not preferable. The RuO 2 powder can be obtained, for example, by heat treatment of a wet synthesized hydrated RuO 2 powder. In that case, the average particle diameter of the RuO 2 powder is preferably 7 nm or more and 30 nm or less. The Pb 2 Ru 2 O 6 powder can be obtained, for example, by mixing wet-synthesized Ru (OH) 4 powder and PbO powder and subjecting them to heat treatment. The average particle diameter of the Pb 2 Ru 2 O 6 powder is preferably 5 nm or more and 500 nm or less. More preferably, the average particle diameter of the Pb 2 Ru 2 O 6 powder is 5 nm or more and 50 nm or less.
The content of such ruthenium oxide-based conductive material powder may be appropriately selected according to the resistance value to be formed, but the total content is 5% by mass or more and 30% by mass or less with respect to 100% by mass of the thick film resistance paste. Is preferred. The inclusion of the ruthenium oxide-based conductive powder forms a conductive path in the resistor, but if the content of the ruthenium oxide-based conductive powder is less than 5% by mass, the resistance value is excessively increased, and in some cases, electricity does not flow. Not desirable because If the content of the ruthenium oxide-based conductive material powder exceeds 30% by mass, the conductive path may be too large to obtain a sufficient resistance value, which is not preferable. More preferably, the content of the ruthenium oxide based conductive material powder is 5 mass% or more and 9.3 mass% or less in total with respect to 100 mass% of the thick film resistance paste.
３．ガラスフリット
　本発明におけるガラスフリットの組成は特に限定されず、一般的な組成の中から誘電体シートの組成に応じて好ましい組成を選択すれば良い。ガラスフリットの平均粒径は０．１μｍ以上５μｍ以下であり、好ましくは０．１μｍ以上３μｍ以下である。本発明において、ガラスフリットの平均粒径が５μｍより大きくなると、焼成された厚膜抵抗体の面積抵抗値が低くなり、かつ面積抵抗値のバラつきが大きくなって歩留まりが低下したり、負荷特性が低下したりするなどの不具合が生じる可能性が高くなるため好ましくない。平均粒径が０．１μｍ未満の場合は、粘度が高くなり過ぎるうえ、非常に取扱い難くなるため好ましくない。
　このようなガラスフリットの含有量は、形成する抵抗値に応じて適宜選定すれば良いが、厚膜抵抗ペースト１００質量％に対し、１５質量％以上７０質量％以下とするのが好ましい。ガラスフリットと導電物粉末との配合量により厚膜抵抗体の抵抗値を変化させることができるが、ガラスフリットの含有量が１５質量％未満であると、導電経路を阻害するガラス量が少な過ぎて十分な抵抗値を示すことができない場合があるため好ましくない。ガラスフリットの含有量が７０質量％を超えると、抵抗値が高くなり過ぎ、場合によっては電気が流れない場合があるため好ましくない。 3. Glass Frit The composition of the glass frit in the present invention is not particularly limited, and may be selected from general compositions in accordance with the composition of the dielectric sheet. The average particle diameter of the glass frit is 0.1 μm to 5 μm, preferably 0.1 μm to 3 μm. In the present invention, when the average particle diameter of the glass frit is larger than 5 μm, the area resistance value of the fired thick film resistor becomes low, and the variation of the area resistance value becomes large to lower the yield or the load characteristics. It is not preferable because the possibility of problems such as lowering may increase. If the average particle size is less than 0.1 μm, the viscosity becomes too high and the handling becomes very difficult.
The content of such a glass frit may be appropriately selected in accordance with the resistance value to be formed, but is preferably 15% by mass to 70% by mass with respect to 100% by mass of the thick film resistor paste. Although the resistance value of the thick film resistor can be changed by the compounding amount of the glass frit and the conductive material powder, if the content of the glass frit is less than 15% by mass, the amount of glass inhibiting the conductive path is too small. Is not preferable because it may not be able to show a sufficient resistance value. When the content of the glass frit exceeds 70% by mass, the resistance value is too high, and in some cases, electricity may not flow, which is not preferable.
４．厚膜抵抗体用添加物
　本発明の厚膜抵抗ペーストには、ＲｕＯ２粉末などの導電物粉末、ガラスフリットのほかに面積抵抗値や抵抗温度係数の調整、膨張係数の調整、耐電圧性の向上やその他改質を目的とした添加剤を含有させることができる。厚膜抵抗ペーストの添加剤として一般に用いられている、ＭｎＯ２、ＣｕＯ、ＴｉＯ２、Ｎｂ２Ｏ５、Ｔａ２Ｏ５、ＳｉＯ２、Ａｌ２Ｏ３、ＺｒＯ２、ＺｒＳｉＯ４などを好適に用いることができる。
　添加剤の含有量は特に限定されるものではないが、ＲｕＯ２粉末とガラスフリットの合計１００質量部に対して、０．０５質量部以上２０質量部以下とするのが好ましい。添加剤の含有量が０．０５質量部未満であると、添加剤の効果がほとんど表れない場合があるため好ましくない。添加剤の含有量が２０質量部を超えると、厚膜抵抗ペーストの粘度が上がり過ぎたり、焼結過程で含有する銀の偏析が生じやすくなったり、形成する抵抗体の出現抵抗値が不安定になったりする場合があるため好ましくない。 4. Thick Film Resistor Additives The thick film resistor paste of the present invention includes conductive powder such as RuO 2 powder, glass frit, adjustment of area resistance value and temperature coefficient of resistance, adjustment of expansion coefficient, voltage resistance Additives may be added for the purpose of improvement and other modifications. It is preferable to use MnO 2 , CuO, TiO 2 , Nb 2 O 5 , Ta 2 O 5 , SiO 2 , Al 2 O 3 , ZrO 2 , ZrSiO 4 or the like generally used as an additive for thick film resistance pastes. be able to.
The content of the additive is not particularly limited, but is preferably 0.05 parts by mass or more and 20 parts by mass or less with respect to a total of 100 parts by mass of the RuO 2 powder and the glass frit. If the content of the additive is less than 0.05 parts by mass, the effect of the additive may hardly appear, which is not preferable. If the content of the additive exceeds 20 parts by mass, the viscosity of the thick film resistor paste may increase excessively, segregation of silver contained in the sintering process may easily occur, or the appearance resistance value of the formed resistor may be unstable. It is not preferable because it may be
５．樹脂成分
　本発明の厚膜抵抗ペーストは、上記材料の他、溶剤中に樹脂成分を溶解した有機ビヒクルを含有する。本発明は、有機ビヒクルの樹脂、溶剤の種類や配合によって特に限定されない。樹脂成分には、エチルセルロース、マレイン酸樹脂、ロジンなどの一般的な成分を用いることができ、溶剤成分には、ターピネオール、ブチルカルビトール、ブチルカルビトールアセテート等の一般的な成分を用いることができる。これらの配合比は、使用する製品に求められる厚膜抵抗ペーストの粘度に応じて調整される。また、厚膜抵抗ペーストの乾燥を遅らせる目的で沸点が高い溶剤を加えることもできる。
　有機ビヒクルの含有量は特に限定されないが、上記各種含有成分との配合比で好適な粘度とするため、無機原料粉末１００質量部に対し、３０質量部以上１００質量部以下とするのが一般的である。 5. Resin Component In addition to the above materials, the thick film resistor paste of the present invention contains an organic vehicle in which a resin component is dissolved in a solvent. The present invention is not particularly limited by the type and composition of the resin and solvent of the organic vehicle. As the resin component, general components such as ethyl cellulose, maleic acid resin, rosin can be used, and as the solvent component, general components such as terpineol, butyl carbitol, butyl carbitol acetate can be used . These compounding ratios are adjusted according to the viscosity of the thick film resistance paste calculated | required by the product to be used. Also, a solvent having a high boiling point can be added in order to delay the drying of the thick film resistance paste.
Although the content of the organic vehicle is not particularly limited, it is generally 30 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the inorganic raw material powder in order to obtain a suitable viscosity in the compounding ratio with the various components described above. It is.
６．厚膜抵抗ペーストの製造
　本発明の厚膜抵抗ペーストは、銀粉末と酸化ルテニウム系導電物粉末、およびガラスフリットからなる厚膜抵抗体用組成物を有機ビヒクル中に分散させることによって得ることができる。本発明の厚膜抵抗ペーストの製造方法には、通常の厚膜抵抗ペーストを製造するのに最も多く使用されているスリーロールミルのほか、遊星ミル、ビーズミルなどによる製造方法を用いることができ、特に製造方法を限定する必要はない。予め本発明に用いる銀粉末と酸化ルテニウム系導電物粉末、およびガラスフリットを、ボールミルや、らいかい機で混合してから、有機ビヒクル中に分散させることもできる。
　無機原料粉末は、無機原料粉末同士が凝集し、粗大な二次粒子粉末となってしまう場合があるため、そのような粗大粉末を解砕した上で、樹脂成分を溶剤に溶解した有機ビヒクル中に分散することが望ましい。一般に、無機原料粉末の粒径が小さくなると凝集が強くなり、二次粒子を形成し易くなる。 6. Production of Thick Film Resistive Paste The thick film resistive paste of the present invention can be obtained by dispersing a composition for a thick film resistor comprising silver powder, ruthenium oxide based conductive powder and glass frit in an organic vehicle. . In addition to the three-roll mill most commonly used to produce conventional thick film resistor pastes, the method of producing thick film resistor pastes of the present invention can be used with planet mills, bead mills, etc. There is no need to limit the manufacturing method. The silver powder, the ruthenium oxide-based conductive powder, and the glass frit used in the present invention may be previously mixed in a ball mill or a grinder and then dispersed in an organic vehicle.
The inorganic raw material powder may cause aggregation of the inorganic raw material powders to form a coarse secondary particle powder, and therefore, such a coarse powder may be crushed and then the resin component is dissolved in a solvent in an organic vehicle. It is desirable to disperse in In general, when the particle size of the inorganic raw material powder is reduced, the aggregation becomes strong and the secondary particles are easily formed.
　以下、本発明による厚膜抵抗ペーストとその材料である厚膜抵抗体用組成物、及び厚膜抵抗ペーストを用いて形成した厚膜抵抗体の実施例を説明する。なお、本発明はこれらの実施例によって限定されるものではない。
　後述する実施例及び比較例における厚膜抵抗体の膜厚は、触針式の厚さ粗さ計を用いて測定した。また、厚膜抵抗体の抵抗値は、デジタルマルチメータで測定した。
　また、実施例及び比較例における厚膜抵抗体に対するパルストリミングは、２００ｐＦ－０Ωのユニットに２～５ｋＶの電圧で電荷を充電した後、厚膜抵抗体に放電し行った。また、放電前の抵抗値をＲ０、放電後の抵抗値をＲ１として、放電後の抵抗値の変化率を以下の式（１）によって計算した。
パルストリミングによる抵抗値の変化率＝（Ｒ１－Ｒ０）／Ｒ０×１００・・・（１）
　そして、上記式（１）によって計算した抵抗値の変化率をパルストリミングによる調整手法を用いて調整可能な抵抗値の変化量とした。 Hereinafter, examples of the thick film resistor paste according to the present invention, the composition for the thick film resistor which is the material thereof, and the thick film resistor formed using the thick film resistor paste will be described. The present invention is not limited by these examples.
The film thickness of the thick film resistors in Examples and Comparative Examples described later was measured using a stylus type thickness roughness meter. Also, the resistance value of the thick film resistor was measured by a digital multimeter.
In addition, pulse trimming of the thick film resistors in the example and the comparative example was performed by charging a 200 pF-0Ω unit with a voltage of 2 to 5 kV and then discharging the thick film resistors. Moreover, the resistance value before discharge was set to R0, the resistance value after discharge was set to R1, and the change rate of the resistance value after discharge was computed by the following formula | equation (1).
Change rate of resistance value by pulse trimming = (R1-R0) / R0 x 100 ... (1)
Then, the rate of change of the resistance value calculated by the above equation (1) is used as the amount of change of the resistance value that can be adjusted using the adjustment method using pulse trimming.
（比較例１～４）
　厚膜抵抗体用組成物の材料として、平均粒径７ｎｍの酸化ルテニウム粉末、平均粒径５０ｎｍのルテニウム酸鉛粉末、ガラスフリットＡ（ＰｂＯ：５０質量％－ＳｉＯ２：３５質量％－Ｂ２Ｏ３：１０質量％－Ａｌ２Ｏ３：５質量％）、ガラスフリットＢ（ＳｉＯ２：３５質量％－Ｂ２Ｏ３：２０質量％－Ａｌ２Ｏ３：５質量％－ＣａＯ：５質量％－ＢａＯ：２０質量％－ＺｎＯ：１５質量％）、厚膜抵抗体用添加物として酸化ニオブを、有機ビヒクルにはターピネオールとエチルセルロース及びステアリン酸を準備した。各材料を表１に示す配合で混合し、厚膜抵抗体用組成物、厚膜抵抗ペーストを作製した。その際、比較例１～４では、夫々、形成される厚膜抵抗体の面積抵抗値の数値範囲が広くなるように材料の配合量を調整した。その結果、比較例１～４では、夫々、形成された厚膜抵抗体の面積抵抗値が１ｋΩ、１０ｋΩ、１１０ｋΩ、８００ｋΩになった。
　また、厚膜抵抗ペーストを作製した際に適度な粘度になるように配合した結果、有機ビヒクルの配合量は３５質量％程度の量となった。本比較例では、スリーロールミルを用いて厚膜抵抗ペーストを作製した。これらの厚膜抵抗ペーストを純度９６質量％のアルミナ基板上に印刷、乾燥、焼成して厚膜抵抗体を形成し、評価した。
　予めアルミナ基板に焼成して形成された１質量％のＰｄ、９９質量％のＡｇの電極上に、作製した厚膜抵抗体ペーストを印刷し、１５０℃×５分の条件で乾燥させた後、ピーク温度８５０℃×９分、トータル３０分熱処理するように構成されたベルト炉を用いて焼成し厚膜抵抗体を形成した。厚膜抵抗体は、サイズが、抵抗体幅１ｍｍ、抵抗体長さ１ｍｍ、厚さ７μｍとなるように印刷し、焼成後、最終的な膜厚を確認した。各種評価結果を表１に示す。なお、表１中に示す抵抗値の変化率（％）の負の値は、低下方向に変化する抵抗値の変化率を示している。また、本願においては、低下方向に変化する抵抗値の変化率の絶対値を、抵抗値の低下率と定義する。 (Comparative Examples 1 to 4)
Ruthenium oxide powder having an average particle diameter of 7 nm, lead ruthenate powder having an average particle diameter of 50 nm, glass frit A (PbO: 50% by mass-SiO 2 : 35% by mass-B 2 O) 3 : 10% by mass-Al 2 O 3 : 5% by mass, glass frit B (SiO 2 : 35% by mass-B 2 O 3 : 20% by mass-Al 2 O 3 : 5% by mass-CaO: 5% by mass -BaO: 20% by mass-ZnO: 15% by mass), niobium oxide as an additive for a thick film resistor, and terpineol, ethyl cellulose and stearic acid as organic vehicles. Each material was mixed by the composition shown in Table 1, and a composition for a thick film resistor and a thick film resistor paste were produced. At that time, in Comparative Examples 1 to 4, the compounding amounts of the materials were adjusted such that the numerical value range of the area resistance value of the formed thick film resistors became wide. As a result, in Comparative Examples 1 to 4, the area resistance values of the formed thick film resistors were 1 kΩ, 10 kΩ, 110 kΩ, and 800 kΩ, respectively.
Moreover, as a result of mix | blending so that it might become a suitable viscosity when producing a thick film resistance paste, the compounding quantity of the organic vehicle became the quantity of about 35 mass%. In this comparative example, a three roll mill was used to prepare a thick film resistor paste. These thick film resistor pastes were printed, dried and fired on an alumina substrate having a purity of 96% by mass to form and evaluate thick film resistors.
The prepared thick film resistor paste is printed on an electrode of 1% by mass of Pd and 99% by mass of Ag previously formed by firing on an alumina substrate and dried at 150 ° C. for 5 minutes, The thick film resistor was formed by firing using a belt furnace configured to perform heat treatment for 30 minutes in total for a peak temperature of 850 ° C. × 9 minutes. The thick film resistor was printed so that the size was 1 mm in the width of the resistor, 1 mm in the length of the resistor, and 7 μm in thickness, and the final film thickness was confirmed after firing. Various evaluation results are shown in Table 1. In addition, the negative value of the change rate (%) of resistance value shown in Table 1 has shown the change rate of the resistance value which changes to a fall direction. Further, in the present application, the absolute value of the change rate of the resistance value changing in the decreasing direction is defined as the decrease rate of the resistance value.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（比較例５～８）
　比較例５、６の厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体は、比較例１～４の厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体における無機成分のうち、酸化ルテニウム粉末を平均粒径３０ｎｍの粉末とした以外は、比較例１～４と略同様に製造した。
　また、比較例７、８の厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体は、比較例１～４の厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体における無機成分のうち、比較例７では平均粒径０．０８μｍ、比較例８では平均粒径５．５μｍの銀粉末を、導電物粉末に加えた以外は、比較例１～４と略同様に製造した。
　各材料の配合量、及び各種評価結果を表２に示す。なお、表２中に示す抵抗値の変化率（％）も、低下方向に変化する抵抗値の変化率を示している。
　各材料を表２に示す配合で混合した結果、比較例５～８では、夫々、形成された厚膜抵抗体の面積抵抗値が０．１０ｋΩ、７０ｋΩ、０．１１ｋΩ、０．１２ｋΩになった。
　また、厚膜抵抗ペーストを作製した際に適切な粘度になるように配合した結果、有機ビヒクルの配合量は３３質量％程度の量となった。 (Comparative Examples 5 to 8)
The compositions for thick film resistors, thick film resistor pastes and thick film resistors of Comparative Examples 5 and 6 are the same as the compositions for thick film resistors of Comparative Examples 1 to 4, inorganic materials for thick film resistor paste and thick film resistors. Among the components, except that the ruthenium oxide powder was changed to a powder having an average particle diameter of 30 nm, it was manufactured in substantially the same manner as Comparative Examples 1 to 4.
The compositions for thick film resistors, thick film resistor pastes and thick film resistors of Comparative Examples 7 and 8 are the compositions for thick film resistors of Comparative Examples 1 to 4, thick film resistor paste and thick film resistors. Among the inorganic components in the above, substantially the same as Comparative Examples 1 to 4 except that a silver powder having an average particle diameter of 0.08 μm in Comparative Example 7 and an average particle diameter of 5.5 μm in Comparative Example 8 was added to the conductive material powder. Manufactured.
The blending amounts of the respective materials and the various evaluation results are shown in Table 2. The rate of change (%) in resistance shown in Table 2 also indicates the rate of change in resistance that changes in the decreasing direction.
As a result of mixing each material by the composition shown in Table 2, in Comparative Examples 5 to 8, the sheet resistance values of the formed thick film resistors became 0.10 kΩ, 70 kΩ, 0.11 kΩ, and 0.12 kΩ, respectively. .
Moreover, as a result of mix | blending so that it might become a suitable viscosity when producing a thick film resistance paste, the compounding quantity of the organic vehicle became the quantity of about 33 mass%.
Figure JPOXMLDOC01-appb-T000002
 　なお、表２中、比較例７、８の銀（質量％)の欄における下段の括弧内の数値は、厚膜抵抗体用組成物に対する銀粉末の質量比（質量％）である。
Figure JPOXMLDOC01-appb-T000002
 In Table 2, the numerical values in the lower parentheses in the column of silver (% by mass) of Comparative Examples 7 and 8 are the mass ratio (% by mass) of silver powder to the composition for a thick film resistor.
（実施例１～４）
　実施例１～４の厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体は、比較例１～４の厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体における無機成分のうち、導電物粉末に平均粒径３μｍの銀粉末を加え、その他は比較例１～４と略同様に製造した。各材料の配合量、及び各種評価結果を表３に示す。なお、表３中に示す抵抗値の変化率（％）も、低下方向に変化する抵抗値の変化率を示している。
　また、各材料を表３に示す配合で混合した際、実施例１～４では、夫々、形成される厚膜抵抗体の面積抵抗値の数値範囲が広くなるように材料の配合量を調整した。その結果、実施例１～４では、夫々、形成された厚膜抵抗体の面積抵抗値が０．４５ｋΩ、４．２ｋΩ、１５ｋΩ、１２０ｋΩになった。
　また、厚膜抵抗ペーストを作製した際に適切な粘度になるように配合した結果、有機ビヒクルの配合量は４０質量％程度の量となった。 (Examples 1 to 4)
The compositions for thick film resistors, thick film resistor pastes and thick film resistors of Examples 1 to 4 are the same as the compositions for thick film resistors of Comparative Examples 1 to 4, inorganic materials for thick film resistor paste and thick film resistors. Among the components, silver powder having an average particle diameter of 3 μm was added to the conductive powder, and the other components were manufactured in substantially the same manner as Comparative Examples 1 to 4. The compounding quantity of each material and various evaluation results are shown in Table 3. The rate of change (%) in resistance shown in Table 3 also indicates the rate of change in resistance that changes in the decreasing direction.
Moreover, when each material was mixed by the mixing | blending shown in Table 3, in Examples 1-4, the compounding quantity of the material was adjusted so that the numerical range of the area resistance value of the thick film resistor formed might become wide, respectively. . As a result, in Examples 1 to 4, the sheet resistance values of the formed thick film resistors became 0.45 kΩ, 4.2 kΩ, 15 kΩ, and 120 kΩ, respectively.
Moreover, as a result of mix | blending so that it might become a suitable viscosity when producing a thick film resistance paste, the compounding quantity of the organic vehicle became the quantity of about 40 mass%.
Figure JPOXMLDOC01-appb-T000003
 　なお、表３中、銀（質量％)の欄における下段の括弧内の数値は、厚膜抵抗体用組成物に対する銀粉末の質量比（質量％）である。
Figure JPOXMLDOC01-appb-T000003
 In Table 3, the numerical values in the lower parentheses in the column of silver (% by mass) are the mass ratio (% by mass) of silver powder to the composition for a thick film resistor.
（実施例５～１１）
　実施例５、６の厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体は、実施例１～４の厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体における無機成分のうち、酸化ルテニウム粉末を平均粒径３０ｎｍの粉末とした以外は、実施例１～４と略同様に製造した。
　また、実施例７の厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体は、実施例１～４の厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体における無機成分のうち、導電物粉末に平均粒径３μｍの銀粉末を、本発明の厚膜抵抗体用組成物における銀粉末の含有範囲の下限値１６質量％に近い値で含有させた以外は、実施例１～４と略同様に製造した。
　また、実施例８、９の厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体は、実施例１～４の厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体における無機成分のうち、実施例８では平均粒径０．１μｍ、実施例９では平均粒径５．０μｍの銀粉末を、導電性粉末に加えた以外は、実施例１～４と略同様に製造した。
　また、実施例１０の厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体は、実施例１～４の厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体における無機成分のうち、導電物粉末に平均粒径３μｍの銀粉末を、本発明の厚膜抵抗ペーストにおける銀粉末の含有範囲の下限値１０質量％に近い値で含有させた以外は、実施例１～４と略同様に製造した。
　また、実施例１１の厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体は、実施例１～４の厚膜抵抗体用組成物、厚膜抵抗ペースト及び厚膜抵抗体における無機成分のうち、酸化ルテニウム粉末を、本発明の厚膜抵抗ペーストにおける酸化ルテニウム粉末の含有範囲の上限値３０質量％に近い値で含有させた以外は、実施例１～４と略同様に製造した。
　各材料の配合量、及び各種評価結果を表４に示す。なお、表４中に示す抵抗値の変化率（％）も、低下方向に変化する抵抗値の変化率を示している。
　各材料を表４に示す配合で混合した結果、実施例５～１１では、夫々、形成された厚膜抵抗体の面積抵抗値が０．０７ｋΩ、１５ｋΩ、０．０８ｋΩ、０．０８ｋΩ、２０ｋΩ、０．０９ｋΩ、０．０８ｋΩになった。
　また、厚膜抵抗ペーストを作製した際に適切な粘度になるように配合した結果、有機ビヒクルの配合量は実施例５、６、７、９では３０～３１質量％程度、実施例８では３４質量％程度、実施例１０では３７質量％程度の量となった。また、実施例１１では、酸化ルテニウム粉末を、本発明の厚膜抵抗ペーストにおける酸化ルテニウム粉末の含有範囲の上限値３０質量％に近い値で含有させるとともに、銀粉末も相当量含有させたため、有機ビヒクルの配合量が２２質量％程度と、実施例および比較例のうちで最少量となった。 (Examples 5 to 11)
The compositions for thick film resistors, thick film resistor pastes and thick film resistors of Examples 5 and 6 are the same as the compositions for thick film resistors of Examples 1 to 4, inorganic materials for thick film resistor paste and thick film resistors. Among the components, manufacture was substantially the same as in Examples 1 to 4 except that the ruthenium oxide powder was changed to a powder having an average particle diameter of 30 nm.
Further, the composition for a thick film resistor, the thick film resistor paste and the thick film resistor of Example 7 are the same as those of the compositions for a thick film resistor, the thick film resistor paste and the thick film resistor of Examples 1 to 4. Among the components, it is carried out except that a silver powder having an average particle diameter of 3 μm is contained in the conductive material powder at a value close to the lower limit 16 mass% of the content range of the silver powder in the composition for thick film resistors of the present invention Manufactured substantially as in Examples 1-4.
The compositions for thick film resistors, thick film resistor pastes and thick film resistors of Examples 8 and 9 are the compositions for thick film resistors of Examples 1 to 4, thick film resistor paste and thick film resistors. Among the inorganic components in Example 1, substantially the same as Examples 1 to 4 except that silver powder having an average particle diameter of 0.1 μm in Example 8 and an average particle diameter of 5.0 μm in Example 9 was added to the conductive powder. Manufactured.
Further, the composition for thick film resistor, thick film resistor paste and thick film resistor of Example 10 are the same as the composition for thick film resistor, thick film resistor paste and thick film resistor of Examples 1 to 4. Among the components, Example 1 to Example 1 except that silver powder having an average particle diameter of 3 μm was contained in the conductive powder at a value close to the lower limit 10% by mass of the content range of silver powder in the thick film resistor paste of the present invention Manufactured substantially as in 4.
Further, the composition for a thick film resistor, the thick film resistor paste and the thick film resistor of Example 11 are the same as the compositions for the thick film resistor, the thick film resistor paste and the thick film resistor of Examples 1 to 4, respectively. Among the components, the same preparation as in Examples 1 to 4 was carried out except that ruthenium oxide powder was contained at a value close to the upper limit value of 30% by mass of the content range of ruthenium oxide powder in the thick film resistor paste of the present invention. .
The blending amounts of the respective materials and the various evaluation results are shown in Table 4. The change rate (%) of the resistance value shown in Table 4 also indicates the change rate of the resistance value changing in the decreasing direction.
As a result of mixing each material by the composition shown in Table 4, in Examples 5 to 11, the area resistance value of the formed thick film resistor is respectively 0.07 kΩ, 15 kΩ, 0.08 kΩ, 0.08 kΩ, 20 kΩ, It became 0.09kΩ and 0.08kΩ.
Moreover, as a result of blending so as to obtain an appropriate viscosity when producing a thick film resistance paste, the blending amount of the organic vehicle is about 30 to 31 mass% in Examples 5, 6, 7, 9 and 34 in Example 8. The amount was about mass%, and in Example 10, about 37 mass%. Further, in Example 11, the ruthenium oxide powder is contained at a value close to the upper limit 30 mass% of the content range of the ruthenium oxide powder in the thick film resistor paste of the present invention, and a considerable amount of silver powder is also contained. The blending amount of the vehicle was about 22% by mass, which was the smallest among the examples and the comparative examples.
　なお、表４中、銀（質量％)の欄における下段の括弧内の数値は、厚膜抵抗体用組成物に対する銀粉末の質量比（質量％）である。 In Table 4, the numerical values in the lower parentheses in the column of silver (% by mass) are the mass ratio (% by mass) of silver powder to the composition for a thick film resistor.
パルストリミングによる調整手法を用いた厚膜抵抗体における抵抗値の変化量の評価
　表３および表４の実施例１～１１に示したように、導電物粉末を酸化ルテニウムとルテニウム酸鉛の混合粉末からなる酸化ルテニウム系導電物粉末と平均粒径が０．１μｍ以上５．０μｍ以下の範囲内の銀粉末とすることにより、パルストリミングの電圧負荷による抵抗値の変化量としての抵抗値の低下率が、導電物粉末に銀を含有しない表１および表２の比較例１～６や、導電物粉末に銀粉末を含有するものの、銀粉末の平均粒径が０．１μｍ以上５．０μｍ以下の範囲を外れた比較例７、８に比べて増大していることが分かる。このため、本発明の厚膜抵抗体用組成物、厚膜抵抗ペーストを用いて製造した厚膜抵抗体によれば、銀粉末を含有しない従来の厚膜抵抗体や、銀粉末を含有するものの、銀粉末の平均粒径が０．１μｍ以上５．０μｍ以下の範囲を外れた厚膜抵抗体に比べて、パルストリミングによる調整手法を用いて調整可能な抵抗値の変化量としての抵抗値の低下率を増大させることができる。 Evaluation of the amount of change in resistance value of a thick film resistor using a pulse trimming adjustment method As shown in Examples 1 to 11 of Tables 3 and 4, the conductive powder is a mixed powder of ruthenium oxide and lead ruthenate. The reduction rate of the resistance value as the amount of change of the resistance value due to the voltage load of the pulse trimming by setting the ruthenium oxide type conductive material powder comprising the above and the silver powder having an average particle diameter in the range of 0.1 μm to 5.0 μm. However, although silver powder is not contained in the conductive substance powder in Comparative Examples 1 to 6 of Tables 1 and 2 and silver powder is contained in the conductive substance powder, the average particle diameter of the silver powder is 0.1 μm to 5.0 μm. It can be seen that it is increased as compared with Comparative Examples 7 and 8 outside the range. Therefore, according to the thick film resistor composition of the present invention and the thick film resistor manufactured using the thick film resistor paste, the conventional thick film resistor not containing silver powder or the one containing silver powder Of the resistance value as the amount of change of the resistance value that can be adjusted using the adjustment method by pulse trimming as compared with the thick film resistor in which the average particle diameter of the silver powder is out of the range of 0.1 μm to 5.0 μm. The rate of decline can be increased.
　本発明の厚膜抵抗体用組成物、厚膜抵抗ペースト及び、厚膜抵抗体は、抵抗体形成時におけるパルストリミングによる調整手法を用いて調整可能な抵抗値の変化量として抵抗値の低下率を増大させることができるため、プリントヘッド用抵抗体、チップ抵抗器、ハイブリッドＩＣ、または、抵抗ネットワーク等の電子部品を製造する分野で、歩留まりよく生産性を高くすることができ有用である。 The composition for a thick film resistor, the thick film resistor paste, and the thick film resistor according to the present invention have a decrease rate of the resistance value as a change amount of the resistance value which can be adjusted using an adjustment method by pulse trimming at the time of forming the resistor. In the field of manufacturing electronic parts such as print head resistors, chip resistors, hybrid ICs, or resistor networks, it is possible to increase productivity with high yield, which is useful.

Claims (9)

  1. 　酸化ルテニウムとルテニウム酸鉛の混合粉末からなる酸化ルテニウム系導電物粉末と、ガラスフリットを含有する厚膜抵抗体用組成物において、
    　１６質量％以上３３質量％以下の銀粉末を更に含有し、有機ビヒクルを加えた厚膜抵抗ペーストを焼結して厚膜抵抗体を形成したときの、該厚膜抵抗体におけるパルストリミングによる調整手法を用いて調整可能な抵抗値の低下率が５％より大きくなるようにしたことを特徴とする厚膜抵抗体用組成物。     In a ruthenium oxide based conductive powder comprising a mixed powder of ruthenium oxide and lead ruthenate, and a composition for a thick film resistor containing a glass frit,
    Adjustment by pulse trimming in a thick film resistor when a thick film resistor is formed by further sintering a thick film resistor paste containing 16 mass% to 33 mass% silver powder and adding an organic vehicle What is claimed is: 1. A composition for a thick film resistor, characterized in that the reduction rate of resistance value that can be adjusted by a method is set to be more than 5%.
  2. 　前記銀粉末の平均粒径が０．１μｍ以上５μｍ以下であり、
    　前記酸化ルテニウム系導電物粉末の平均粒径が１ｎｍ以上５００ｎｍ以下であり、
    　前記ガラスフリットの平均粒径が０．１μｍ以上５μｍ以下であることを特徴とする請求項１に記載の厚膜抵抗体用組成物。     The average particle diameter of the silver powder is 0.1 μm to 5 μm,
    The average particle diameter of the ruthenium oxide based conductive material powder is 1 nm or more and 500 nm or less,
    The composition for a thick film resistor according to claim 1, wherein an average particle diameter of the glass frit is 0.1 μm to 5 μm.
  3. 　前記酸化ルテニウム粉末の平均粒径が７ｎｍ以上３０ｎｍ以下であることを特徴とする請求項１又は２に記載の厚膜抵抗体用組成物。 The composition for a thick film resistor according to claim 1 or 2, wherein an average particle diameter of the ruthenium oxide powder is 7 nm or more and 30 nm or less.
  4. 　前記ルテニウム酸鉛粉末の平均粒径が５ｎｍ以上５０ｎｍ以下であることを特徴とする請求項１～３のいずれかに記載の厚膜抵抗体用組成物。 The composition for a thick film resistor according to any one of claims 1 to 3, wherein an average particle diameter of the lead ruthenate powder is 5 nm or more and 50 nm or less.
  5. 　請求項１～４のいずれかに記載の厚膜抵抗体用組成物に、更に有機ビヒクルを加えてなることを特徴とする厚膜抵抗ペースト。 A thick film resistor paste comprising the composition for a thick film resistor according to any one of claims 1 to 4 further comprising an organic vehicle.
  6. 　前記銀粉末を１０質量％以上２０質量％以下、前記酸化ルテニウム系導電物粉末を総量で５質量％以上３０質量％以下、前記ガラスフリットを１５質量％以上７０質量％以下含有し、残部が前記有機ビヒクルからなることを特徴とする請求項５に記載の厚膜抵抗ペースト。 10% by mass or more and 20% by mass or less of the silver powder, 5% by mass or more and 30% by mass or less of the ruthenium oxide-based conductive powder, and 15% by mass or more and 70% by mass or less of the glass frit; The thick film resistor paste according to claim 5, comprising an organic vehicle.
  7. 　前記酸化ルテニウム系導電物粉末を総量で５質量％以上９．３質量％以下含有することを特徴とする請求項６に記載の厚膜抵抗ペースト。 The thick film resistor paste according to claim 6, wherein the ruthenium oxide conductive powder is contained in a total amount of 5% by mass or more and 9.3% by mass or less.
  8. 　請求項５～７のいずれかに記載の厚膜抵抗ペーストの焼結体であることを特徴とする厚膜抵抗体。 A thick film resistor characterized in that it is a sintered body of the thick film resistor paste according to any one of claims 5 to 7.
  9. 　パルストリミングによる調整手法を用いて調整可能な抵抗値の低下率が５％より大きいことを特徴とする請求項８に記載の厚膜抵抗体。 9. The thick film resistor according to claim 8, wherein the decrease rate of the adjustable resistance value is larger than 5% by using the adjustment method by pulse trimming.
PCT/JP2018/034854 2017-09-22 2018-09-20 Composition for thick film resistor, thick film resistance paste, and thick film resistor WO2019059290A1 (en)

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