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
• • 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
  • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/40—Glass
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • 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
  • 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
• • 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
  • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits 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
  • H01C17/06573—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the permanent binder
  • H01C17/06586—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the permanent binder composed of organic material
• • 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

Definitions

• the present invention relates to a resistor paste used as a resistor material such as a thick film chip resistor or a hybrid IC, and more particularly to a resistor paste not containing lead and a resistor produced by firing the paste.
• a thick film method in which a film is formed using a resistance paste containing a film forming material and a thin film method in which a film forming material is formed by sputtering or the like are generally used.
• the thick film method is to form a resistor by printing a resistor paste on a ceramic substrate and then firing it. This method is inexpensive and has high productivity required for film formation. It is widely used for manufacturing resistors included in electronic components such as chip resistors and hybrid ICs.
• the resistive paste used in the above thick film system contains conductive particles and glass frit, and an organic vehicle for making them suitable for printing.
• conductive particles ruthenium dioxide (RuO 2 ) or pyrochlore-type ruthenium-based oxides (Pb 2 Ru 2 O 7-X , Bi 2 Ru 2 O 7 ) are generally used.
• the reason why the Ru-based oxide is used as the conductive particles is mainly because the resistance value changes gently with respect to the concentration of the conductive particles.
• a large amount of lead such as lead borosilicate glass (PbO—SiO 2 —B 2 O 3 ) and lead aluminoborosilicate glass (PbO—SiO 2 —B 2 O 3 —Al 2 O 3 ) is used.
• Including lead borosilicate glass is used. The reason why the lead borosilicate glass is used for the glass frit in this way is that it has good wettability with the Ru-based oxide, has a thermal expansion coefficient close to that of the substrate, and has a suitable viscosity during firing.
• Patent Document 1 discloses a thick film resistor excellent in electrical characteristics by mixing a refined ruthenium oxide powder, a glass containing PbO, and niobium oxide (Nb 2 O 5 ) together with an inert vehicle. A technique for producing a resistive paste is disclosed.
• Nb 2 O 5 when used as an additive, the characteristics can be improved with a small addition amount, but the resistance value is also greatly changed, so that there is a problem that it is difficult to adjust the resistance value.
• lead-free electronic components have been promoted in consideration of environmental protection, and lead-free solder pastes are also required.
• electronic components made from the above-mentioned resistance paste are becoming increasingly smaller and have higher performance, and as a result, resistance resistors with higher resistance and lower current noise are produced. What can be done is required.
• the present invention has been made in view of the above situation, and can form a lead-free thick film resistor excellent in electrical characteristics capable of suppressing current noise while having a high resistance value.
• An object is to provide a lead-free resistance paste.
• the present inventor uses a lead-free oxide containing ruthenium in conductive particles by including a specific additive in the resistance paste. At the same time, it has been found that a resistor having good electrical characteristics can be produced even when a lead-free glass frit is used, and the present invention has been completed.
• the resistance paste provided by the present invention is a resistance paste containing conductive particles made of ruthenium dioxide, a glass frit containing no lead, an organic vehicle, and an additive, wherein the additive has a specific surface area. It is characterized by containing 5% by mass or more and 12% by mass or less of amorphous silica of 60 m 2 / g or more and 125 m 2 / g or less.
• a resistance paste capable of producing a thick film resistor excellent in electrical characteristics capable of suppressing current noise to a low level while having a high resistance value without causing environmental pollution due to lead. Can do.
• the resistance paste of the present invention There is no restriction
• the oxide obtained by a general manufacturing method can be used.
• the average particle diameter by diameter is preferably 1.0 ⁇ m or less.
• the glass frit contained in the resistance paste is not particularly limited as long as it does not contain lead.
• borosilicate glass, aluminoborosilicate glass, borosilicate alkaline earth glass, borosilicate alkali glass, borosilicate zinc glass, borosilicate bismuth glass, or the like can be used.
• D50 diameter measured by laser diffraction particle size distribution measurement of glass frit to minimize the conductive path in the thick film resistor and suppress variations in resistance value and current noise of the thick film resistor as much as possible. Is preferably 5 ⁇ m or less.
• the organic vehicle contained in the resistance paste may be one that is usually used in resistance pastes, for example, a resin in which a resin such as ethyl cellulose, butyral, or acrylic is dissolved in a solvent such as terpineol or butyl carbitol acetate. Preferably used.
• the resistance paste further contains 5% by mass to 12% by mass of amorphous silica (SiO 2 ) having a specific surface area of 60 m 2 / g or more and 125 m 2 / g or less as an additive.
• Amorphous silica has a function of increasing current resistance by increasing the resistance value of the resistor formed by firing.
• the reason why the specific surface area of amorphous silica is limited to 60 m 2 / g or more and 125 m 2 / g or less is that current noise (dB) is hardly negative when the specific surface area is less than 60 m 2 / g, and conversely 125 m 2 / g.
• the content of amorphous silica is set to 5% by mass or more and 12% by mass or less with respect to the resistance paste. This is because the current noise (dB) is unlikely to become negative even if the value exceeds the value.
• the method for producing the resistance paste of the above-described embodiment of the present invention is not particularly limited, and a predetermined amount of the components of the resistance paste described above is weighed into a commercially available kneading apparatus such as a roll mill, and kneaded. Can be produced. At that time, the mixing ratio of the conductive particles and the glass frit is preferably about 5/95 to 50/50 in terms of the ratio of the conductive particles / glass frit on a mass basis. Further, the method for manufacturing the resistor is not particularly limited, and the resistor can be formed by the same method as the conventional one using the resistor paste of the embodiment of the present invention as a material.
• the above-mentioned resistance paste is applied to a normal substrate such as an alumina substrate by screen printing or the like, dried, and then fired at a peak temperature of about 800 to 900 ° C. using a belt furnace or the like, thereby lead-free. Can be formed.
• the resistor paste according to the embodiment of the present invention is conventionally used in various ways such as dispersants and plasticizers that are conventionally used to adjust the electrical characteristics of thick film resistors. You may add an additive as needed.
• Conductive particles, glass frit, organic vehicle, and additives are mixed at various blending ratios to prepare multiple resistor paste samples, which are then fired to form thick film resistors and their electrical properties was evaluated.
• RuO 2 powder having a BET diameter of 40 nm prepared by roasting ruthenium hydroxide was prepared as the conductive particles.
• the glass frit was prepared by mixing, melting, quenching and pulverizing by a general method, 10 mass% SrO-43 mass% SiO 2 -16 mass% B 2 O 3 -4 mass% Al 2 O 3 -20 mass
• a glass frit having a composition of% ZnO-7 mass% Na 2 O and having a D50 of 1.9 ⁇ m as measured by laser diffraction particle size distribution was prepared.
• amorphous SiO 2 having specific surface areas of 3 m 2 / g, 30 m 2 / g, 60 m 2 / g, 80 m 2 / g, and 125 m 2 / g are prepared as additives, and organic vehicles are used as organic vehicles.
• an alumina substrate on which two electrodes having an interelectrode distance of 1 mm are formed using AgPd paste is prepared for the resistance paste of each sample, and the two electrodes are connected on the alumina substrate.
• the film was screen-printed to a width of 1 mm, dried at 150 ° C. for 10 minutes, and then fired in a belt furnace at a peak temperature of 850 ° C. for 9 minutes.
• the electrical characteristics (resistance value, current noise) of the thick film resistor thus fabricated were measured.
• the composition of the resistance paste and the characteristics of the resistor obtained by each paste are shown in Table 1 below.
• the resistance value was measured by a 4-terminal method using a Model 2001 Multimeter manufactured by KEITHLEY, and the current noise was measured by applying a 1/10 W using a noise meter Model 315C manufactured by Quan-Tech.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Manufacturing & Machinery (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Dispersion Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Materials Engineering (AREA)
• Electromagnetism (AREA)
• Conductive Materials (AREA)
• Non-Adjustable Resistors (AREA)
• Glass Compositions (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Apparatuses And Processes For Manufacturing Resistors (AREA)

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• 2016
  • 2016-10-20 JP JP2016205989A patent/JP6708093B2/ja active Active
• 2017
  • 2017-10-19 KR KR1020197011628A patent/KR102384488B1/ko active IP Right Grant
  • 2017-10-19 WO PCT/JP2017/037905 patent/WO2018074562A1/ja active Application Filing
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