CN109844871B - Resistor paste, resistor, electronic component, and method for producing lead-free resistor - Google Patents
Resistor paste, resistor, electronic component, and method for producing lead-free resistor Download PDFInfo
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- CN109844871B CN109844871B CN201780064365.2A CN201780064365A CN109844871B CN 109844871 B CN109844871 B CN 109844871B CN 201780064365 A CN201780064365 A CN 201780064365A CN 109844871 B CN109844871 B CN 109844871B
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- 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
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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
- C03C8/24—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
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- 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
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- 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
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- 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
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- 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
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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)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Electromagnetism (AREA)
- Conductive Materials (AREA)
- Non-Adjustable Resistors (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Apparatuses And Processes For Manufacturing Resistors (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a lead-free thick film resistor with high resistance value and good electrical characteristics with small current noise, a lead-free resistor paste as a material thereof, an electronic component and a method for manufacturing the lead-free resistor. An electrical resistance paste comprising: conductive particles containing ruthenium dioxide, a lead-free glass frit, an organic vehicle, and an additive, wherein the additive contains 5 to 12 mass% of a specific surface area of 60m2More than 125 m/g2Amorphous silicon dioxide of not more than g.
Description
Technical Field
The present invention relates to a resistor paste used as a material for a resistor such as a thick film chip resistor or a hybrid Integrated Circuit (IC), particularly a lead-free resistor paste, and a resistor manufactured by firing the resistor paste.
Background
Conventionally, as a method for forming a resistor film of an electronic component, there are generally known: a thick film system using a resistance paste containing a film forming material and a thin film system formed by sputtering or the like a film forming material. Among these, the thick film method is a method of forming a resistor by printing a resistor paste on a ceramic substrate and then firing the printed paste, and is widely used for manufacturing a resistor included in an electronic component such as a chip resistor or a hybrid IC because the equipment required for film formation is inexpensive and the productivity is high.
The resistor paste used in the thick film method includes: conductive particles, glass frit, and an organic vehicle for forming these into a paste suitable for printing. As a conductivityParticles, typically ruthenium dioxide (RuO)2) Or pyrochlore type ruthenium oxide (Pb)2Ru2O7-X、Bi2Ru2O7). The reason why the Ru-based oxide is used as the conductive particles is mainly as follows: the resistance value changes gently with respect to the concentration of the conductive particles.
In addition, as the glass frit, lead borosilicate glass (PbO-SiO) was used2-B2O3) Or aluminoborosilicate lead glass (PbO-SiO)2-B2O3-Al2O3) And lead borosilicate glass containing a large amount of lead. The reason why the lead borosilicate based glass is used as such a frit is that: has good wettability with Ru-based oxide, a thermal expansion coefficient close to that of the substrate, and a suitable viscosity during firing.
In the above-mentioned resistor paste, various additives have been contained in order to improve the characteristics of the resistor after film formation. For example, patent document 1 discloses ruthenium oxide powder, PbO-containing glass, and niobium oxide (Nb)2O5) And mixing the paste with an inert carrier to prepare a resistive paste for a thick film resistor having excellent electrical characteristics.
Documents of the prior art
Patent document
Patent document 1: japanese patent publication No. 63-035081
Disclosure of Invention
Problems to be solved by the invention
However, when Nb is used2O5In the case of the additive, the characteristic can be improved by a small amount of the additive, but since the resistance value also changes significantly, there is a problem that the adjustment of the resistance value is difficult. In recent years, lead-free electronic components have been developed in consideration of environmental protection, and lead-free resistor pastes are also required. Further, electronic components and the like produced using the above-mentioned resistance paste as a material tend to be more and more compact and have higher performance, and accordingly, there is a demand for a resistance paste capable of producing a resistor having a high resistance value and a low current noise.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a lead-free resistor paste which can form a lead-free thick film resistor having a high resistance value and excellent electrical characteristics in which current noise can be suppressed.
Means for solving the problems
The present inventors have made extensive studies on a lead-free resistor paste that can achieve the above object, and as a result, have found that a resistor having excellent electrical characteristics can be produced by adding a specific additive to the resistor paste even when a lead-free oxide containing ruthenium is used as the conductive particles and a lead-free glass frit is used, and have completed the present invention.
That is, the present invention provides a resistor paste comprising: conductive particles comprising ruthenium dioxide, a lead-free glass frit, an organic vehicle, and an additive, and the resistance paste is characterized in that: the additive has a specific surface area of 60m in an amount of 5 to 12 mass%2More than 125 m/g2Amorphous silicon dioxide of not more than g.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a resistor paste is provided which can produce a thick film resistor having high resistance and excellent electrical characteristics capable of suppressing current noise without causing environmental pollution due to lead.
Detailed Description
Hereinafter, embodiments of the resistive paste according to the present invention will be described. The form of ruthenium dioxide as the conductive particles contained in the resistance paste according to the embodiment of the present invention is not particularly limited, and oxides obtained by a general production method can be used. Among them, in order to suppress unevenness in resistance value and current noise of the thick film resistor formed by firing as much as possible, it is preferable that the conductive path in the thick film resistor is made fine, and therefore, it is preferable that the average particle diameter of the oxide particles using the blauer-Emmett-Teller (BET) diameter is 1.0 μm or less.
The composition of the glass frit contained in the resistance paste is not particularly limited as long as it does not contain lead. For example, borosilicate glass, aluminoborosilicate glass, borosilicate alkaline earth glass, borosilicate alkali glass, borosilicate zinc glass, borosilicate bismuth glass, or the like can be used. As described above, in order to make the conductive path in the thick film resistor fine and suppress the variation in the resistance value of the thick film resistor and the current noise as much as possible, it is preferable that D50 (median diameter) obtained by laser diffraction type particle size distribution measurement of the glass frit is 5 μm or less.
The organic vehicle contained in the resistor paste may be a vehicle generally used in resistor pastes, and for example, a vehicle obtained by dissolving a resin such as ethyl cellulose, butyral, or acrylic in a solvent such as terpineol or butyl carbitol acetate is preferably used.
The resistance paste further contains 5 to 12 mass% of a specific surface area of 60m2More than 125 m/g2Amorphous silicon dioxide (SiO) of less than g2) As an additive. The amorphous silicon dioxide has a function of increasing the resistance value of the resistor formed by firing and reducing current noise. The specific surface area of the amorphous silica was defined to be 60m2More than 125 m/g2The reason for the following/g is: if the specific surface area is less than 60m2The current noise (dB) is hard to become negative when the current is/g, whereas the current noise (dB) is hard to become negative when the current exceeds 125m2The viscosity of the resistor paste becomes too high per gram to prepare the resistor paste. The reason why the content of the amorphous silicon dioxide is 5 mass% or more and 12 mass% or less with respect to the resistance paste is: if the mass% is less than 5%, the current noise (dB) is less negative, whereas if the mass% exceeds 12%, the current noise (dB) is less negative.
The method for producing the electrical resistance paste according to the embodiment of the present invention is not particularly limited, and the electrical resistance paste can be produced by weighing and charging predetermined amounts of the components of the electrical resistance paste in a commercially available kneading apparatus such as a roll mill, and kneading the components. In this case, the mixing ratio of the conductive particles and the glass frit is preferably about 5/95 to 50/50 in terms of a mass-based conductive particle/glass frit ratio. The method for producing the resistor is not particularly limited, and the resistor paste according to the embodiment of the present invention can be used as a material and formed by the same method as before. For example, the resistance paste can be 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 ℃ using a conveyor oven or the like to form a lead-free resistor.
The resistor paste according to the embodiment of the present invention may further contain, in addition to the above-mentioned essential components, various additives such as a dispersant and a plasticizer, which have been conventionally used for adjusting the electrical characteristics of the thick film resistor, as required.
Examples
A plurality of resistance paste samples were prepared by mixing conductive particles, glass frit, organic vehicle and additives at various mixing ratios, and these samples were calcined to form thick-film resistors and their electrical characteristics were evaluated. Specifically, conductive particles were prepared by baking ruthenium hydroxide to prepare RuO having a BET diameter of 40nm2And (3) powder. Glass frit the following glass frit was prepared, which had a D50 of 1.9 μm as measured by laser diffraction particle size distribution: has 10 mass% SrO-43 mass% SiO prepared by mixing, melting, quenching, crushing and the like by a usual method2-16 mass% B2O3-4 mass% Al2O3-20 mass% ZnO-7 mass% Na2Composition of O.
The specific surface areas of the additives were 3m each2/g、30m2/g、60m2/g、80m2G and 125m2Five amorphous SiO of/g2The organic vehicle is prepared from ethyl cellulose and terpineol as main components. These RuOs should be2The powder, glass frit, additives and organic vehicle were weighed in various blending ratios and kneaded by a triple roll mill. Thus, resistance pastes of samples 1 to 17 were prepared.
Next, an alumina substrate on which two electrodes having an inter-electrode distance of 1mm were formed using AgPd paste was prepared for the resistance paste of each sample, the resistance paste was screen-printed on the alumina substrate so as to connect the two electrodes to each other to have a width of 1mm, dried at 150 ℃ for 10 minutes, and then calcined at a peak temperature of 850 ℃ for 9 minutes in a conveyor furnace. The electrical characteristics (resistance value, current noise) of the thick film resistor produced in the above manner were measured. The composition of the resistive paste and the characteristics of the resistor obtained from each paste are shown in table 1 below. The resistance value was measured by a four-terminal method using a Model 2001Multimeter (Model 2001Multimeter) manufactured by KEITHLEY (KEITHLEY), and the current noise was measured under 1/10W application using a noise tester Model 315C (Model 315C) manufactured by quentack (quant-Tech).
[ Table 1]
Note) the samples with x in the table are comparative examples.
As is clear from table 1, it is clear that: even when using a fluid containing cheap RuO2When the thick film resistor is formed by adding the conductive particles and the lead-free glass frit according to (1), the specific surface area is 60m within the range defined in the present invention2More than 125 m/g2Amorphous SiO of less than g2As an additive with or without addition of amorphous SiO2Or adding amorphous SiO by a scheme not satisfying the main conditions of the present invention2Current noise can be reduced compared to the case of (1).
Claims (4)
1. A resistance paste containing conductive particles including ruthenium dioxide, a lead-free glass frit, an organic vehicle, and an additive, and characterized in that: the additive has a specific surface area of 60m in an amount of 5 to 12 mass%2More than 125 m/g2Amorphous silica having a Braun's diameter of 1.0 μm or less.
2. A lead-free resistor obtained by firing the resistor paste according to claim 1.
3. An electronic component, comprising the resistor according to claim 2.
4. A method for manufacturing a lead-free resistor, comprising: a resistor body is produced by firing the resistor paste according to claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016205989A JP6708093B2 (en) | 2016-10-20 | 2016-10-20 | Resistor paste and resistor produced by firing the paste |
| JP2016-205989 | 2016-10-20 | ||
| PCT/JP2017/037905 WO2018074562A1 (en) | 2016-10-20 | 2017-10-19 | Resistive paste and resistor produced by firing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109844871A CN109844871A (en) | 2019-06-04 |
| CN109844871B true CN109844871B (en) | 2021-06-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201780064365.2A Active CN109844871B (en) | 2016-10-20 | 2017-10-19 | Resistor paste, resistor, electronic component, and method for producing lead-free resistor |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6708093B2 (en) |
| KR (1) | KR102384488B1 (en) |
| CN (1) | CN109844871B (en) |
| TW (1) | TWI746670B (en) |
| WO (1) | WO2018074562A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7251068B2 (en) * | 2018-07-31 | 2023-04-04 | 住友金属鉱山株式会社 | Composition for thick film resistor, paste for thick film resistor, and thick film resistor |
| JP7183507B2 (en) * | 2019-02-13 | 2022-12-06 | 住友金属鉱山株式会社 | Composition for thick film resistor, paste for thick film resistor, and thick film resistor |
| JP7347057B2 (en) * | 2019-09-18 | 2023-09-20 | 住友金属鉱山株式会社 | Composition for thick film resistor and paste for thick film resistor |
| JP7347056B2 (en) * | 2019-09-18 | 2023-09-20 | 住友金属鉱山株式会社 | Composition for thick film resistor and method for producing the same, paste for thick film resistor and method for producing the same |
| CN112010558B (en) * | 2020-09-03 | 2022-09-27 | 山东华菱电子股份有限公司 | Lead-free silicate glass glaze raw material composition, lead-free silicate glass glaze and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1290942A (en) * | 1999-10-04 | 2001-04-11 | 株式会社东芝 | Voltage nonlinear resistor and its producing method |
| CN1290943A (en) * | 1999-10-04 | 2001-04-11 | 株式会社东芝 | Voltage nonlinear resistor and its producing method |
| CN101990522A (en) * | 2008-04-18 | 2011-03-23 | E.I.内穆尔杜邦公司 | Lead-free resistive compositions having ruthenium oxide |
| CN101990689A (en) * | 2008-04-18 | 2011-03-23 | E.I.内穆尔杜邦公司 | Surface-modified ruthenium oxide conductive material, lead-free glass(es), thick film resistor paste(s), and devices made therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6335081A (en) | 1986-07-30 | 1988-02-15 | Rhythm Watch Co Ltd | Light quantity correcting device for video camera |
| US8642682B2 (en) * | 2004-04-30 | 2014-02-04 | Kureha Corporation | Resin composition for encapsulation and semiconductor unit encapsulated with resin |
| JP6084397B2 (en) * | 2012-08-17 | 2017-02-22 | 太陽ホールディングス株式会社 | Inorganic particle-containing paste for sintering and coating formed product |
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2016
- 2016-10-20 JP JP2016205989A patent/JP6708093B2/en active Active
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2017
- 2017-10-19 WO PCT/JP2017/037905 patent/WO2018074562A1/en active Application Filing
- 2017-10-19 KR KR1020197011628A patent/KR102384488B1/en active IP Right Grant
- 2017-10-19 CN CN201780064365.2A patent/CN109844871B/en active Active
- 2017-10-20 TW TW106136193A patent/TWI746670B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1290942A (en) * | 1999-10-04 | 2001-04-11 | 株式会社东芝 | Voltage nonlinear resistor and its producing method |
| CN1290943A (en) * | 1999-10-04 | 2001-04-11 | 株式会社东芝 | Voltage nonlinear resistor and its producing method |
| CN101990522A (en) * | 2008-04-18 | 2011-03-23 | E.I.内穆尔杜邦公司 | Lead-free resistive compositions having ruthenium oxide |
| CN101990689A (en) * | 2008-04-18 | 2011-03-23 | E.I.内穆尔杜邦公司 | Surface-modified ruthenium oxide conductive material, lead-free glass(es), thick film resistor paste(s), and devices made therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018074562A1 (en) | 2018-04-26 |
| KR102384488B1 (en) | 2022-04-08 |
| JP2018067478A (en) | 2018-04-26 |
| CN109844871A (en) | 2019-06-04 |
| JP6708093B2 (en) | 2020-06-10 |
| KR20190072540A (en) | 2019-06-25 |
| TWI746670B (en) | 2021-11-21 |
| TW201823380A (en) | 2018-07-01 |
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