WO2021221174A1 - 厚膜抵抗ペースト、厚膜抵抗体、及び電子部品 - Google Patents

厚膜抵抗ペースト、厚膜抵抗体、及び電子部品 Download PDF

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Publication number
WO2021221174A1
WO2021221174A1 PCT/JP2021/017300 JP2021017300W WO2021221174A1 WO 2021221174 A1 WO2021221174 A1 WO 2021221174A1 JP 2021017300 W JP2021017300 W JP 2021017300W WO 2021221174 A1 WO2021221174 A1 WO 2021221174A1
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Prior art keywords
mass
thick film
oxide
glass
powder
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English (en)
French (fr)
Japanese (ja)
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真規 安藤
崇仁 永野
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Sumitomo Metal Mining Co Ltd
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Sumitomo Metal Mining Co Ltd
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Priority to JP2022518161A priority Critical patent/JP7622738B2/ja
Priority to CN202180031480.6A priority patent/CN115516578A/zh
Priority to KR1020227035721A priority patent/KR102851511B1/ko
Priority to US17/921,736 priority patent/US12304860B2/en
Publication of WO2021221174A1 publication Critical patent/WO2021221174A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/14—Compositions for glass with special properties for electro-conductive glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
    • C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
    • C03C3/074—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
    • C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
    • C03C3/074—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron containing zinc
    • C03C3/0745—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron containing zinc containing more than 50% lead oxide, by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
    • C03C3/108—Glass compositions containing silica with 40% to 90% silica, by weight containing lead containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • 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
    • 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 or green body
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits or green body characterised by the resistive component
    • H01C17/06553—Precursor compositions therefor, e.g. pastes, inks, glass frits or green body characterised by the resistive component composed of a combination of metals and oxides
    • 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
    • H01C7/003—Thick film resistors
    • 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
    • H01C7/06—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 including means to minimise changes in resistance with changes in temperature

Definitions

  • the present invention relates to a thick film resistance paste, and more specifically, contains a ruthenium oxide-containing glass powder, silver powder, palladium powder, or both powders, and has no cracks in appearance and is excellent in surge resistance.
  • the present invention relates to a thick film resistor paste capable of forming a thick film resistor, particularly used for low resistance, a thick film resistor using the thick film resistor paste, and an electronic component provided with the thick film resistor.
  • Thick film resistance paste is generally composed of conductive powder, glass powder, and an organic vehicle for making them into a paste suitable for printing. By printing this thick film resistor paste in an arbitrary pattern and sintering glass at a high temperature of usually 800 to 1000 ° C., it is used as a thick film resistor that constitutes an electronic component such as a thick film chip resistor. ing.
  • the conductive powder ruthenium oxide powder and lead ruthenate powder are widely used because the resistance value can be gradually changed by changing the mixing ratio with the glass powder.
  • Patent Document 1 a vehicle using ethyl cellulose as a binder and toluene and alcohol as a solvent is added to a mixture using mulite as an inorganic particle, lead borosilicate glass as a glass particle, and ruthenium dioxide as a conductive particle.
  • the technique of the thick film resistor formed by using the resistance paste thus obtained is described. Further, when a low resistance value of less than 100 ⁇ appears, silver, palladium, or both powders are further contained as the conductive powder.
  • Patent Document 2 describes a technique for a thick film resistance paste in which a composition for a thick film resistor containing a ruthenium oxide-based conductive powder and a glass frit, further containing silver powder and adding an organic vehicle. Have been described.
  • thick-film resistors are required to have improved electrical characteristics.
  • An excellent thick film resistor is required.
  • a momentary high voltage (surge voltage) is applied to the thick film resistor, it usually shows a negative resistance value change, but it is desirable that the resistance value change amount is small.
  • Such a negative resistance value change is considered to be the effect of heat generation when a voltage is applied.
  • the glass powders are bonded to each other at the time of sintering, but the softening of the glass powders is limited to the surface layer.
  • the thick film resistor after sintering the thick film resistor paste there is a dielectric layer corresponding to the glass particle size.
  • the conductive powder is distributed around this dielectric layer to make the thick film resistor conductive.
  • ruthenium oxide powder is preferably used as the conductive powder, and when lower resistance is formed, silver powder, palladium powder, or a mixed powder of both is further contained. .. Since ruthenium oxide is not sinterable, cracks are likely to occur especially in a low resistance resistor containing a large amount of ruthenium oxide.
  • Patent Document 3 further includes a polycarboxylic acid-based dispersant in a resistance paste containing a carbon-based conductive powder, pt-butylphenol, and a substituted monovalent phenol resin obtained by a condensation reaction with formaldehyde.
  • a polycarboxylic acid-based dispersant in a resistance paste containing a carbon-based conductive powder, pt-butylphenol, and a substituted monovalent phenol resin obtained by a condensation reaction with formaldehyde.
  • An object of the present invention is to use a thick film resistance paste, which has no abnormal cracks in appearance and has sufficient surge resistance, which is particularly excellent for low resistance, while using lead borosilicate glass.
  • An object of the present invention is to provide a thick film resistor and an electronic component provided with the thick film resistor.
  • the thick film resistance paste according to the present invention contains silver powder, palladium powder, or a mixed powder thereof, ruthenium oxide-containing glass powder, and an organic vehicle, and the ruthenium oxide-containing glass powder contains ruthenium oxide.
  • 10% by mass or more and 60% by mass or less and the glass composition is 3% by mass or more and 60% by mass or less of silicon oxide and 30% by mass or more and 90% by mass or less of lead oxide with respect to 100% by mass of the glass component. It is characterized in that it contains 5% by mass or more and 50% by mass or less of boron oxide, and the total content of silicon oxide, lead oxide and boron oxide is 50% by mass or more with respect to 100% by mass of the glass component.
  • the average particle size of the ruthenium oxide-containing glass powder is 5 ⁇ m or less.
  • the thick film resistor according to the present invention is characterized by being made of a sintered body of any of the above-mentioned thick film resistor pastes of the present invention.
  • the low resistance electronic component according to the present invention is characterized by comprising the above-mentioned thick film resistor of the present invention.
  • a thick film resistor paste and a thick film resistor which can reduce the occurrence rate of cracks generated on the surface of the resistor as compared with the conventional one and have sufficient surge resistance, especially excellent for low resistance.
  • electronic components can be provided.
  • FIG. 3 is a metal micrograph of the surface of the resistor according to Comparative Example 1.
  • the thick film resistance paste of the present embodiment contains silver powder, palladium powder, or a mixed powder of both, ruthenium oxide-containing glass powder, and an organic vehicle.
  • silver powder palladium powder
  • ruthenium oxide-containing glass powder ruthenium oxide-containing glass powder
  • organic vehicle an organic vehicle
  • Conducting material As the conductor in the thick film resistance paste of the present invention, silver, palladium, or a mixture thereof and ruthenium oxide are used.
  • a general thick film resistance paste has a structure in which a conductive material and glass are contained in powder form, respectively.
  • ruthenium oxide powder which is a conductive material, is not used alone. , It has a structure using ruthenium oxide-containing glass powder obtained by crushing ruthenium oxide-containing glass produced by using ruthenium oxide and glass.
  • the particle size of ruthenium oxide used to form the ruthenium oxide-containing glass powder is not particularly limited, but it is desirable that the particle size has a specific surface area of 5 m 2 / g or more. If the specific surface area is less than 5 m 2 / g, the particle size of ruthenium oxide is too large, which may reduce the uniformity of the conductive region in the thick film resistor and deteriorate the surge resistance. Further, in the thick film resistance paste of the present invention, in order to efficiently develop a low resistance value, silver powder, palladium powder, or a mixed powder of both is contained.
  • the particle size of the silver powder and the palladium powder is not particularly limited, but for electronic parts that are becoming smaller, the silver powder has an average particle size of 1 ⁇ m or more and 10 ⁇ m or less, and the palladium powder has an average particle size of 0.2 ⁇ m or more and 1 ⁇ m or less. It is desirable to use.
  • the type of silver powder or palladium powder and the average particle size may be appropriately selected according to the size and characteristics of the resistor to be used.
  • the glass component used for the ruthenium oxide-containing glass in the thick film resistance paste of the present invention contains silicon oxide (SiO 2 ), lead oxide (PbO) and boron oxide (B 2 O 3 ).
  • silicon oxide SiO 2
  • PbO lead oxide
  • B 2 O 3 boron oxide
  • magnesium oxide (MgO) calcium oxide (CaO), barium oxide (BaO), strontium oxide (SrO), cadmium oxide (CdO), tin oxide (SnO), zinc oxide (ZnO), bismuth oxide (Bi 2 O) 3 ) and the like may be contained.
  • aluminum oxide (Al 2 O 3 ) may be contained.
  • SiO 2 is a component that serves as a skeleton of the glass component of the present invention, and the blending amount is 3% by mass or more and 60% by mass or less with respect to 100% by mass of the glass component contained in the ruthenium oxide-containing glass. If it is more than 60% by mass, the softening point of the formed glass becomes too high. Further, if it is less than 3% by mass, chemically stable glass cannot be obtained.
  • (Lead oxide: PbO) PbO has a function of lowering the softening point and a function of promoting wetting with ruthenium oxide and enhancing dispersibility.
  • the blending amount is 30% by mass or more and 90% by mass or less with respect to 100% by mass of the glass component contained in the ruthenium oxide-containing glass. If it is less than 30% by mass, the softening point of the formed glass becomes too high. On the other hand, if it is more than 90% by mass, it becomes difficult to obtain a chemically stable glass state.
  • B 2 O 3 is a component that forms the skeleton of the glass component of the present invention together with SiO 2 , and has an effect of lowering the softening point of the glass to be formed.
  • the blending amount is 5% by mass or more and 50% by mass or less with respect to 100% by mass of the glass component contained in the ruthenium oxide-containing glass. If it is less than 5% by mass, the toughness of the glass to be formed is lowered, cracks are likely to occur, and the laser trimming property is deteriorated. Further, if it is more than 50% by mass, phase separation of the glass component is likely to occur, and the water resistance is also lowered.
  • Total content of essential glass components The total content of SiO 2 , PbO, and B 2 O 3 is 50% by mass or more with respect to 100% by mass of the glass component contained in the ruthenium oxide-containing glass. If it is less than 50% by mass, it is difficult to stably form the glass, and it is difficult to satisfy the surge resistance in the electrical characteristics of the thick film resistor of the present invention.
  • an oxide in addition to the above-mentioned essential glass components, in order to improve various properties, an oxide can be further contained as a glass component as long as the properties of the ruthenium oxide-containing glass are not deteriorated.
  • Al 2 O 3 , MgO, CaO, BaO, SrO, CdO, SnO, ZnO, Bi 2 O 3 and the like can be contained.
  • the blending amount of these glass components is 20% by mass or less with respect to 100% by mass of the glass component contained in the ruthenium oxide-containing glass.
  • the mixing ratio of ruthenium oxide, which is a conductor, and the glass component is 10% by mass or more and 60% by mass with respect to 100% by mass of the ruthenium oxide-containing glass composition. % Or less, and the glass component is 40% by mass or more and 90% by mass or less. If the ruthenium oxide is less than 10% by mass, the resistance value of the produced ruthenium oxide-containing glass powder becomes too high, and the ruthenium oxide shows almost no conductivity. On the other hand, if it is more than 60% by mass, the glass component cannot cover the ruthenium oxide powder, and the ruthenium oxide-containing glass becomes brittle.
  • the resistance value of the thick film resistor can be adjusted to be close to the target resistance value.
  • the ruthenium oxide-containing glass is pulverized so that the average particle size is 5 ⁇ m or less. If the average particle size is larger than 5 ⁇ m, the uniformity of the thick film resistor is lowered, the surge resistance is poor, and the surface of the thick film resistor may be cracked, which is not preferable.
  • a crushing method a ball mill, a planetary mill, a bead mill or the like can be used.
  • the average particle size means the median diameter
  • the powder to be measured is ultrasonically dispersed in an aqueous solution of sodium hexametaphosphate (2 g / L), and a particle size distribution meter (HPA9320-100X, Microtrac) using a pure water solvent is used. It is a numerical value measured using (Bell).
  • the thick film resistor paste of the present invention further contains conductive-free borosilicate glass for the purpose of adjusting and improving the resistance value, TCR, and other properties of the thick film resistor, and commonly used additives. You may let me. Further, a dispersant may be contained as an additive in order to improve the dispersibility.
  • the main additives are niobium oxide (Nb 2 O 5 ), tantalum oxide (Ta 2 O 5 ), titanium oxide (TiO 2 ), copper oxide (CuO), manganese oxide (MnO 2 ), zirconium oxide (ZrO 2). ), Aluminum oxide (Al 2 O 3 ) and the like.
  • the content of the additive can be adjusted according to the desired improvement characteristics, but is preferably 10% by mass or less in the total amount of 100% by mass of the inorganic substances.
  • Organic vehicle used in the thick film resistance paste of the present invention is not particularly limited, and a solvent such as tarpineol used in a general resistance paste in which a resin such as ethyl cellulose or rosin is dissolved may be used. can.
  • the blending amount of the organic vehicle may be appropriately adjusted according to the printing method and the like, but is generally 20% by mass or more and 50% by mass or less with respect to 100% by mass of the total amount of the resistance paste.
  • a mixed powder of silver powder, palladium powder, or both, a glass powder containing ruthenium oxide, and an organic vehicle are mixed by adding lead borosilicate glass powder, additives, etc., if necessary, and a thick film resistance paste is added.
  • the method for producing the above is not particularly limited, and a general three-roll mill, a bead mill, or the like can be used.
  • a thick film resistor can be obtained by printing the obtained thick film resistor paste on a ceramic substrate, removing the organic solvent by a drying treatment, and then firing at a temperature of, for example, 800 ° C. to 900 ° C.
  • Example 1 Evaluation of a resistor having an area resistance value of 10 ⁇ A glass material was mixed at a ratio of 60% by mass and ruthenium oxide at a ratio of 40% by mass, melted, and then cooled to prepare ruthenium oxide-containing glass.
  • the glass composition of the produced conductive-containing glass was 33% by mass of SiO 2 , 48% by mass of PbO, 5% by mass of Al 2 O 3 , and 7% by mass of B 2 O 3 with respect to 100% by mass of the glass component.
  • ZnO is 2% by mass
  • CaO is 5% by mass.
  • the obtained ruthenium oxide-containing glass was pulverized with a ball mill so that the average particle size was about 1 ⁇ m.
  • Example 1 28% by mass of ruthenium oxide-containing glass powder, 10% by mass of lead borosilicate glass powder, 32% by mass of palladium-coated silver powder (mass ratio of palladium to silver 30:70), and Mn 2 O 3 as an additive.
  • a thick film resistor composition containing 1% by mass and 1% by mass of Nb 2 O 5 and the balance being an organic vehicle was kneaded with a three-roll mill so that various inorganic materials were dispersed in the organic vehicle.
  • the thick film resistance paste of Example 1 was prepared.
  • SiO 2 was 33% by mass
  • PbO was 48% by mass
  • Al 2 O 3 was 5% by mass
  • B 2 O 3 was 7% by mass with respect to 100% by mass of the glass component.
  • An organic vehicle containing 2% by mass of ZnO and 5% by mass of CaO was used, and 20 parts by mass of ethyl cellulose was dissolved in 100 parts by mass of tarpineol.
  • Table 1 shows the composition of the thick film resistance paste of Example 1 and the composition of the ruthenium oxide-containing glass used for producing the thick film resistance paste.
  • Film thickness measurement For the film thickness, an arbitrary one was selected from the evaluation sample 1 for each alumina substrate using a stylus type surface roughness meter, and the film thickness of each of the five thick film resistors was measured. The average value of the five points was taken as the measured film thickness.
  • TCR Temporal coefficient of resistance
  • Example 2 to 12 The glass material and ruthenium oxide were mixed and melted at the ratios shown in Table 1, and then cooled to prepare ruthenium oxide-containing glass.
  • the contents of SiO 2 , PbO, Al 2 O 3 , B 2 O 3 , ZnO, and CaO with respect to 100% by mass of the glass component are the ratios shown in Table 1.
  • Each of the obtained ruthenium oxide-containing glasses was pulverized with a ball mill so that the average particle size was as shown in Table 1.
  • the composition was kneaded with a three-roll mill so that various inorganic materials were dispersed in the organic vehicle to prepare thick film resistance pastes of Examples 2 to 12.
  • the lead borosilicate glass powder and the organic vehicle have the same composition as that used in Example 1.
  • a thick film resistor of an evaluation sample was prepared by the same method as in Example 1, and the same evaluation as in Example 1 was performed. The results of each evaluation are shown in Table 3.
  • Comparative Example 1 A thick film resistance paste was prepared by a conventional production method in which a conductor and glass were added in powder form without using ruthenium oxide-containing glass.
  • ruthenium oxide powder and glass powder are added without using ruthenium oxide-containing glass powder obtained by crushing ruthenium oxide-containing glass, the electrical characteristics are adjusted to a resistance value suitable for the thick film resistance paste.
  • TCR time difference between Comparative Example 1 prepared by the conventional production method, in order to adjust TCR and the like, ruthenium oxide powder, lead ruthenium powder, and ruthenium oxide powder, lead ruthenium powder, and palladium are blended as a conductor in addition to ruthenium oxide powder.
  • the blending amount of the coated silver powder (palladium to silver mass ratio 30:70) and the like was adjusted. That is, 20% by mass of ruthenium oxide powder, 5% by mass of lead ruthenate powder, 42% by mass of silver powder coated with palladium (mass ratio of palladium to silver 30:70), 30% by mass of glass powder, and additives. Mn 2 O 3 is contained in an amount of 1% by mass and Nb 2 O 5 is contained in an amount of 1% by mass, and the balance is composed of an organic vehicle.
  • the thick film paste of Comparative Example 1 was prepared by kneading so as to disperse.
  • the glass composition in the produced thick film resistance paste was 33% by mass of SiO 2 , 47% by mass of PbO, 5% by mass of Al 2 O 3 , and 7 % by mass of B 2 O 3 with respect to 100% by mass of the glass component. %, ZnO is 3% by mass, and CaO is 5% by mass.
  • the organic vehicle has the same composition as that used in Example 1.
  • Table 2 shows the composition of the thick film resistance paste of Comparative Example 1 and the composition of the glass used for producing the thick film resistance paste.
  • a thick film resistor of an evaluation sample was prepared by the same method as in Example 1, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 3, and the surface-observed photographs of the metallurgical microscope are shown in FIG.
  • the composition was kneaded with a three-roll mill so that various inorganic materials were dispersed in the organic vehicle to prepare thick film resistance pastes of Comparative Examples 2 to 10.
  • the lead borosilicate glass powder and the organic vehicle have the same composition as that used in Example 1.
  • a thick film resistor of an evaluation sample was prepared by the same method as in Example 1, and the same evaluation as in Example 1 was performed. The results of each evaluation are shown in Table 3.
  • the thick film resistors of Examples 1 to 12 formed by the thick film resistor paste prepared by using the ruthenium oxide-containing glass powder of the present invention were prepared without using the ruthenium oxide-containing glass powder.
  • the generation of cracks on the surface of the thick film resistor is suppressed, the rate of change in resistance value before and after the electrostatic discharge test is small, and the surge resistance is excellent. It was confirmed that there was.
  • the thick film resistor of Comparative Example 2 formed by the thick film resistance paste obtained by using the ruthenium oxide-containing glass having a content of ruthenium oxide less than the claimed range of the present invention is the resistance value of the conductor-containing glass powder. Was found to be too high and showed little conductivity.
  • the thick film resistor of Comparative Example 3 formed by the thick film resistance paste obtained by using the ruthenium oxide-containing glass having a ruthenium oxide content higher than the claimed range of the present invention had crack-like defects on the surface. Was done.
  • a comparison formed by a thick film resistance paste obtained by using a glass component whose content of silicon oxide, lead oxide, or boron oxide, or the total content of these essential glass components is outside the claims of the present invention. It was confirmed that the thick film resistors of Examples 4 to 10 had a higher rate of change in resistance value before and after the electrostatic discharge test than the thick film resistors of Examples 1 to 12, and were inferior in surge resistance.
  • the thick film resistor formed by using the thick film resistor paste of the present invention is suitable for electronic components that have been miniaturized in recent years because crack generation is suppressed and surge resistance is excellent. It is recognized that it can be used.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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PCT/JP2021/017300 2020-05-01 2021-04-30 厚膜抵抗ペースト、厚膜抵抗体、及び電子部品 Ceased WO2021221174A1 (ja)

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CN202180031480.6A CN115516578A (zh) 2020-05-01 2021-04-30 厚膜电阻糊、厚膜电阻体和电子部件
KR1020227035721A KR102851511B1 (ko) 2020-05-01 2021-04-30 후막 저항 페이스트, 후막 저항체, 및 전자 부품
US17/921,736 US12304860B2 (en) 2020-05-01 2021-04-30 Thick film resistor paste, thick film resistor, and electronic component

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JPS53100496A (en) * 1977-02-15 1978-09-01 Sumitomo Metal Mining Co Method of manufacturing paste for resistance body
JPS6324601A (ja) * 1986-07-17 1988-02-02 松下電器産業株式会社 描画用抵抗体組成物
JPH06140214A (ja) * 1992-10-23 1994-05-20 Sumitomo Metal Mining Co Ltd 厚膜抵抗体ペーストの製造方法および厚膜抵抗体の形成方法
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CN115516578A (zh) 2022-12-23
TW202207244A (zh) 2022-02-16
JPWO2021221174A1 (https=) 2021-11-04
US20230167011A1 (en) 2023-06-01
KR102851511B1 (ko) 2025-08-27

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