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 or green body
  • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits or green body characterised by the resistive component
  • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits or green body characterised by the resistive component composed of oxides
• • 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
  • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits or green body characterised by the resistive component composed of oxides
  • H01C17/0654—Oxides of the platinum group
• • 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
  • 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

Definitions

• the present invention relates to a thick film resistance paste, and more specifically, a thick film resistance paste containing a glass powder containing lead ruthenate as a conductor and capable of forming a thick film resistor particularly excellent in surge resistance. , A thick film resistor using the thick film resistor paste, and an electronic component provided with the thick film resistor.
• the thick film resistance paste is generally composed of a conductive powder, a glass powder, and an organic vehicle for making them into a paste suitable for printing.
• a thick film resistor paste 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.
• the conductive powder ruthenium oxide powder and lead ruthenate powder are widely used because the resistance value can be gradually changed by adjusting 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.
• mulite as an inorganic particle
• lead borosilicate glass as a glass particle
• ruthenium dioxide as a conductive particle.
• Patent Document 2 zircon was used as the inorganic particles, lead borosilicate glass was used as the glass particles, ethyl cellulose was used as the binder, and terpineol and butyl carbitol acetate were used as the solvent in the mixture using ruthenium dioxide as the conductive particles.
• the technique of the resistance paste obtained by adding a vehicle and the thick film resistor formed by using the resistance paste is described.
• thick-film resistors with excellent withstand voltage such as surge resistance.
• the body 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 the dielectric layer to make the thick film resistor conductive. It is considered that when a surge voltage is applied to such a structure, a current flows through the conductive portion, the surrounding area is locally heated, and the resistance value changes.
• TCR indicates the rate of change in resistance value per unit temperature, and is one of the important characteristics of thick film resistors.
• the resistance value of the conductive portion itself changes even if the resistance value change due to heat generation when a surge voltage is applied is suppressed. Therefore, when increasing the amount of lead ruthenate, it is required to bring the TCR close to zero.
• This TCR can be adjusted by adding an additive mainly composed of a metal oxide to the thick film resistor, and examples of the metal oxide include manganese oxide, niobium oxide, and titanium oxide.
• an additive mainly composed of a metal oxide to the thick film resistor, and examples of the metal oxide include manganese oxide, niobium oxide, and titanium oxide.
• An object of the present invention is a thick film resistor paste for a resistor having a small resistance change rate and excellent surge resistance for electronic components that are becoming smaller and smaller, and a thick film resistor using the thick film resistor paste. And an electronic component including the thick film resistor thereof.
• the thick film resistance paste according to the present invention contains a lead ruthenate-containing glass powder and an organic vehicle, and the lead ruthenate-containing glass powder contains 10% by mass or more and 70% by mass or less of lead ruthenate.
• the glass composition contains 3% by mass or more and 60% by mass or less of silicon oxide, 30% by mass or more and 90% by mass or less of lead oxide, and 5% by mass or more and 50% by mass or less of boron oxide with respect to 100% by mass of the glass component.
• 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 lead ruthenate-containing glass powder is 5 ⁇ m or less.
• the thick film resistor according to the present invention is characterized by being composed of a fired body of any of the above-mentioned thick film resistor pastes of the present invention.
• the electric / electronic component according to the present invention is characterized by comprising the above-mentioned thick film resistor of the present invention.
• the thick film resistance paste of the present embodiment contains a lead ruthenate-containing glass powder and an organic vehicle.
• a lead ruthenate-containing glass powder contains a lead ruthenate-containing glass powder and an organic vehicle.
• Lead ruthenate is used as the conductor in the thick film resistance paste of the present invention.
• a general thick film resistance paste has a structure in which a conductor and glass are contained in powder form, respectively.
• lead ruthenate powder which is a conductor, is used alone. Instead, it has a structure containing lead ruthenate-containing glass powder obtained by crushing lead ruthenate-containing glass produced by using lead ruthenate powder which is a conductive material as a part of a raw material.
• the particle size of lead ruthenate used to form the lead ruthenate-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 lead ruthenate is too large, which may reduce the uniformity of the conductive region in the thick film resistor and deteriorate the surge resistance.
• the glass component used for the lead ruthenate-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
• lead oxide PbO
• boron oxide B 2 O 3
• 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
• aluminum oxide Al 2 O 3
• 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 lead ruthenate-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.
• PbO Lead oxide
• 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 lead ruthenate-containing glass. If it is less than 30% by mass, the softening point of the formed glass becomes too high. Further, 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 lead ruthenate-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 lead ruthenate-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 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 lead ruthenate-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 lead ruthenate-containing glass.
• the mixing ratio of lead ruthenate as a conductor and the glass component is 10% by mass of lead ruthenate with respect to 100% by mass of the lead ruthenate-containing glass composition. It is 70% by mass or less and the glass component is 30% by mass or more and 90% by mass or less. If the amount of lead ruthenate is less than 10% by mass, the resistance value of the produced lead ruthenate-containing glass powder becomes too high and shows almost no conductivity. On the other hand, if it is more than 70% by mass, the glass component cannot cover the lead ruthenate powder, and the lead ruthenate-containing glass becomes brittle.
• the lead ruthenate-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, and the effect of improving surge resistance may not be obtained, 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 includes 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. It may be contained. 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 by a printing method or 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.
• the method for producing a thick film resistance paste by mixing lead ruthenate-containing glass and an organic vehicle with the addition of lead borosilicate glass powder, additives and the like as necessary is not particularly limited and is general.
• a 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 an area resistance value of 10 k ⁇ resistor
• a glass material was mixed at a ratio of 63% by mass and lead ruthenate at a ratio of 37% by mass, melted, and then cooled to prepare a lead ruthenate-containing glass.
• the glass composition of the produced lead ruthenate-containing glass was 33% by mass of SiO 2 , 46% 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
• CaO is 6% by mass.
• the obtained lead ruthenate-containing glass was pulverized with a ball mill so that the average particle size was about 1 ⁇ m.
• a thick film resistor composition containing 59% by mass of lead ruthenate-containing glass powder, 1% by mass of Nb 2 O 5 as an additive, and an organic vehicle in the balance, and various inorganic materials are organic vehicles in a three-roll mill.
• the thick film resistance paste of Example 1 was prepared by kneading so as to disperse in the paste.
• As the organic vehicle 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 lead ruthenate-containing glass used for producing the thick film resistance paste.
• Film thickness measurement For the film thickness, use a stylus type surface roughness meter to select an arbitrary one from the evaluation samples for each alumina substrate, measure the film thickness of each of the five thick film resistors, and measure the film thickness. The average value of 5 points was taken as the measured film thickness.
• the SiO 2 30 wt%, a PbO 55 wt%, the Al 2 O 3 5 wt%, the B 2 O 3 The glass material comprising 10 wt%, of the same composition as used in Example 1 Organic
• a glass paste was prepared by kneading with a three-roll mill so as to disperse in the vehicle.
• a glass paste was applied so as to cover the thick film resistor of the evaluation sample, and the sample was dried in a belt furnace having a peak temperature of 150 ° C. for 5 minutes. Then, it was fired in a belt furnace having a peak temperature of 600 ° C. for 5 minutes.
• the resistance value of the thick film resistor coated with glass paste is set as the initial resistance value Rs (t), and the laser trimming device (SL432R, OMRON Laser Front Co., Ltd.) has a resistance value 1.5 times that of Rs (t).
• Laser trimmed with (manufactured by).
• the laser trimming conditions are straight cut, cut speed 100 mm / sec, laser intensity 2 W, and Q rate 6 kHz.
• the resistance value Re (t) after trimming was used, and the ratio of the resistance value deviation before and after trimming was calculated using the following equation (3).
• Resistance value deviation (%) (Re (t) -1.5 x Rs (t)) / Rs (t) x 100 ...
• Example 2 to 12 The glass material and lead ruthenate were mixed and melted at the ratios shown in Table 1, and then cooled to prepare lead ruthenate-containing glass.
• the glass composition of each of the produced lead ruthenate-containing glass is the ratio of the contents of SiO 2 , PbO, Al 2 O 3 , B 2 O 3 , ZnO, and CaO to 100% by mass of the glass component as shown in Table 1. It has become.
• Each of the obtained lead ruthenate-containing glasses was pulverized with a ball mill so that the average particle size was as shown in Table 1.
• a thick film resistor composition containing lead ruthenate-containing glass powder, additives, and organic vehicle in the proportions shown in Table 1 is kneaded with a three-roll mill so that various inorganic materials are dispersed in the organic vehicle. Then, the thick film resistance pastes of Examples 2 to 12 were prepared.
• the organic vehicle has the same composition as that used in Example 1. Further, 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 lead ruthenate and glass, which are conductors, were added in powder form without using lead ruthenate-containing glass.
• lead ruthenate powder and glass powder are added without using lead ruthenate-containing glass powder obtained by crushing lead ruthenate-containing glass, the resistance value is adjusted to be suitable for thick film resistance paste.
• Electrical characteristics (TCR) and the like will be different. Therefore, in Comparative Example 1 prepared by the conventional production method, in order to adjust TCR and the like, ruthenium oxide powder was added as a conductor in addition to ruthenium oxide powder to adjust the blending amount.
• a thick film resistance paste of Comparative Example 1 was prepared by kneading the resistor composition with a three-roll mill so that various inorganic materials were dispersed in the organic vehicle.
• 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.
• 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. Further, 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 resistance paste of Comparative Example 2 was prepared by kneading so as to disperse in the mixture.
• the organic vehicle has 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.
• a thick film resistor composition containing lead ruthenate-containing glass powder, additives, and organic vehicle in the proportions shown in Table 1 is kneaded with a three-roll mill so that various inorganic materials are dispersed in the organic vehicle. Then, the thick film resistance pastes of Comparative Examples 3 to 10 were prepared.
• the organic vehicle has the same composition as that used in Example 1. Further, 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 paste prepared by using the lead ruthenate-containing glass powder of the present invention were prepared without using the lead ruthenate-containing glass powder.
• the rate of change in resistance value before and after the electrostatic discharge test is very low, and it is excellent in surge resistance (high voltage resistance).
• Comparative Examples 2, 6, 8 and 10 formed by a thick film resistance paste obtained by using lead ruthenate-containing glass prepared by using a glass component having a boron oxide content less than the claimed range of the present invention. It was found that the thick film resistor had insufficient trimming property and was not suitable for commercialization.
• the thick film resistor of Comparative Example 3 formed by the thick film resistance paste obtained by using the lead ruthenate-containing glass having a lead ruthenate content less than the claimed range of the present invention is a lead ruthenate-containing glass powder. It was found that the resistance value of was too high and showed almost no conductivity. Further, the thick film resistors of Comparative Example 4 formed by the thick film resistance paste obtained by using the lead ruthenate-containing glass having a lead ruthenate content higher than the claimed range of the present invention are the thick film resistors of Examples 1 to 12. It was confirmed that the resistance value change rate before and after the electrostatic discharge test was higher than that of the thick film resistor, and the surge resistance was inferior.
• Comparative Example 5 formed by a thick film resistance paste obtained by using a glass component in which the content of silicon oxide or lead oxide, or the total content of these essential glass components is outside the claims of the present invention.
• the thick-film resistor of Comparative Example 9 formed by the thick-film resistor of No. 7 and the thick-film resistor paste obtained by using a glass component having a boron oxide content higher than the claimed range of the present invention is also used in Examples 1 to 12. It was confirmed that the resistance value change rate before and after the electrostatic discharge test was higher and the surge resistance was inferior to that of the thick film resistor.
• the thick film resistor formed by using the thick film resistor paste of the present invention has excellent trimming property and surge resistance, and can be suitably used for electronic components that have been miniaturized in recent years. Is recognized.

Landscapes

• Engineering & Computer Science (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Organic Chemistry (AREA)
• Electromagnetism (AREA)
• Manufacturing & Machinery (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Dispersion Chemistry (AREA)
• Non-Adjustable Resistors (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=78332085

Family Applications (1)

Country Status (6)

Cited By (2)

Citations (4)

Family Cites Families (10)

• 2021
  • 2021-04-30 CN CN202180032157.0A patent/CN115461825A/zh active Pending
  • 2021-04-30 JP JP2022518160A patent/JP7622737B2/ja active Active
  • 2021-04-30 WO PCT/JP2021/017299 patent/WO2021221173A1/ja not_active Ceased
  • 2021-04-30 US US17/922,110 patent/US12283408B2/en active Active
  • 2021-04-30 KR KR1020227035720A patent/KR102820136B1/ko active Active
  • 2021-05-03 TW TW110115861A patent/TWI869591B/zh active

Patent Citations (4)

Also Published As

Similar Documents

Legal Events