WO2018150890A1 - Resistor composition, resistor paste containing same, and thick-film resistor using same - Google Patents

Resistor composition, resistor paste containing same, and thick-film resistor using same Download PDF

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Publication number
WO2018150890A1
WO2018150890A1 PCT/JP2018/003405 JP2018003405W WO2018150890A1 WO 2018150890 A1 WO2018150890 A1 WO 2018150890A1 JP 2018003405 W JP2018003405 W JP 2018003405W WO 2018150890 A1 WO2018150890 A1 WO 2018150890A1
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WO
WIPO (PCT)
Prior art keywords
resistor
glass powder
mass
resistance
less
Prior art date
Application number
PCT/JP2018/003405
Other languages
French (fr)
Japanese (ja)
Inventor
勝弘 川久保
Original Assignee
住友金属鉱山株式会社
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Publication date
Application filed by 住友金属鉱山株式会社 filed Critical 住友金属鉱山株式会社
Priority to CN201880011579.8A priority Critical patent/CN110291599B/en
Priority to KR1020197024326A priority patent/KR102420736B1/en
Publication of WO2018150890A1 publication Critical patent/WO2018150890A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
    • 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
    • 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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • 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
    • C03C8/22—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions containing two or more distinct frits having different compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • 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 resistor paste for forming a resistor used for manufacturing an electronic component such as a chip resistor, a hybrid IC, or a resistor network, a resistor composition that constitutes the resistor paste, and And a thick film resistor formed using the resistor paste.
  • a thick film resistor used for manufacturing an electronic component such as a chip resistor, a hybrid IC, or a resistor network is formed by printing and baking a resistor paste on a ceramic substrate.
  • a composition mainly composed of ruthenium-based conductive particles represented by ruthenium oxide and glass powder as conductive particles is widely used.
  • the thick film resistor is a relatively thick resistor obtained by printing and baking using a resistor paste as described above, and is very thin formed by sputtering or vacuum evaporation. It is a general name used in distinction from thin film resistors.
  • the resistance composition of such a ruthenium-based conductive particle and glass powder can change the resistance value depending on its blending ratio. That is, when the mixing ratio of the ruthenium-based conductive particles is increased, the resistance value is decreased, and when the mixing ratio of the ruthenium-based conductive particles is decreased, the resistance value is increased.
  • a desired resistance value appears by adjusting the mixing ratio of the ruthenium-based conductive particles and the glass powder.
  • ruthenium-based conductive particles most frequently used in thick film resistors include ruthenium oxide (RuO 2 ) having a rutile crystal structure and lead ruthenate (Pb 2 Ru 2 O having a pyrochlore crystal structure). 7 ). These are all oxides showing metallic conductivity.
  • the glass powder used for the thick film resistor is generally a glass having a softening point lower than the firing temperature of the resistor paste.
  • many glass powders containing lead oxide (PbO) are used. It was used. The reason for this is that PbO has the effect of lowering the softening point of the glass powder, so it can be easily changed to a softening point suitable for thick film resistors over a wide range by changing the content rate, and PbO is contained. This makes it possible to produce glass powder with relatively high chemical durability, and high insulation and excellent pressure resistance.
  • the composition for a resistor composed of ruthenium-based conductive particles and glass powder
  • a low resistance value a large amount of ruthenium-based conductive particles and a small amount of glass powder are blended, and when a high resistance value is desired.
  • the resistance value is adjusted by blending a large amount of glass powder with few ruthenium-based conductive particles.
  • the resistance temperature coefficient tends to be a large positive value in the low resistance region where many ruthenium-based conductive particles are blended, and the resistance temperature coefficient becomes negative in the high resistance region where there are few ruthenium-based conductive particles blended.
  • the temperature coefficient of resistance represents the rate of change of the resistance value with respect to the temperature change, and is one of the important characteristics of the resistor.
  • Lead ruthenate (Pb 2 Ru 2 O 7 ) used as such a combination has a higher specific resistance than ruthenium oxide (RuO 2 ), and has a high resistance temperature coefficient and a positive value when a thick film resistor is formed. There is a feature to become. For this reason, lead ruthenate (Pb 2 Ru 2 O 7 ) has often been used as conductive particles in the high resistance region.
  • a material containing a lead component in both conductive particles and glass powder has been used in a conventional resistor composition having a particularly high resistance value region.
  • the lead component is undesirable from the viewpoint of influence on the human body and pollution, and is a regulated substance under the RoHS directive and the like, and there is a strong demand for the development of a resistor composition that does not contain lead.
  • Patent Document 1 discloses a resistor paste using calcium ruthenate, strontium ruthenate, and barium ruthenate as a ruthenium-based conductive particle as a resistor composition. Conductive particles having an average particle diameter of 5 ⁇ m or more and 50 ⁇ m or less are used. However, usually, when conductive particles having a large particle size are used, the formed resistor has a large current noise, and it may not be possible to obtain good load characteristics. It has a problem that it is difficult to keep it low.
  • Patent Document 2 proposes a method for suppressing decomposition of ruthenium-based conductive particles not containing lead by using glass in which ruthenium oxide is dissolved.
  • the amount of ruthenium oxide dissolved in the glass powder is greatly affected by variations in manufacturing conditions and greatly fluctuates, there is a problem that the resistance value is not stable.
  • Patent Document 3 discloses a resistor composition of bismuth ruthenate and glass containing bismuth as ruthenium-based conductive particles, but the resistance temperature coefficient of the resistor formed by this combination has a negative value. Therefore, the temperature coefficient of resistance cannot be set to a value close to 0 within ⁇ 100 ppm / ° C.
  • Patent Document 4 proposes a method of suppressing the decomposition of ruthenium composite oxide into ruthenium oxide by bringing the basicity of glass powder close to the basicity of ruthenium composite oxide and further precipitating a crystal phase in the glass. Yes.
  • This method is characterized by the presence of MSi 2 Al 2 O 8 crystals (M: Ba and / or Sr) in the thick film resistor, but it is difficult to uniformly disperse such crystals. The resistance value may not be stable.
  • Patent Document 5 discloses a thick film resistor containing ruthenium oxide and SiO 2 —B 2 O 3 —K 2 O glass powder.
  • the thick film resistor has a negative resistance temperature coefficient. It is stated that it should not. However, since 1 part by weight or more of the alkali metal oxide is contained in the glass composition, the insulating property of the glass is lowered, and the load characteristics of the resistor may be lowered.
  • the resistance temperature coefficient tends to increase to a positive value in the low resistance value region in which many ruthenium-based conductive particles are blended, and the ruthenium-based conductive particles.
  • the temperature coefficient of resistance tends to be negative. Therefore, the temperature coefficient of resistance is adjusted by adding a regulator mainly composed of a metal oxide to the resistor composition, but the resistance temperature coefficient of a negative value is adjusted to the positive side. There are few modifiers and it is very difficult. It is also difficult to adjust the temperature coefficient of resistance, which shows a very large positive value, in the negative direction so as to be close to 0 within ⁇ 100 ppm / ° C.
  • a resistor composition comprising a glass powder containing PbO and ruthenium-based conductive particles that has been used has a large effect of a regulator that adjusts the resistance temperature coefficient, and the range in which the resistance temperature coefficient can be adjusted is wide.
  • the glass powder is not included, the effect of the adjusting agent is small, and the range in which the temperature coefficient of resistance can be adjusted is narrowed. Therefore, in a wide resistance value range, in a combination of glass powder not containing lead and ruthenium-based conductive particles, the temperature coefficient of resistance can be made a value close to 0 within ⁇ 100 ppm / ° C. using a regulator. There is a need.
  • An object of the present invention is to provide a resistor composition and a resistor paste to be formed, and to provide a thick film resistor using them.
  • a resistor composition comprising, as main components, ruthenium-based conductive particles containing no lead and at least two types of glass powder containing no lead.
  • One glass powder is a Si—B—Al—Ba—Zn—O-based glass powder containing SiO 2 , B 2 O 3 , Al 2 O 3 , BaO, ZnO, and the glass component includes the Si—B— 5% by mass or more and 12% by mass or less of B 2 O 3 is contained with respect to 100% by mass of the total amount of the Al—Ba—Zn—O-based glass powder, and the other glass powder is SiO 2 , B 2 O 3 , Al Si-B-Al-Ba-O-based glass powder containing 2 O 3 and BaO, whose glass component is 14% by mass or more with respect to 100% by mass of the total amount of the Si-B-Al-Ba-O-based glass powder.
  • the first invention of the present invention is a resistor composition
  • ruthenium-based conductive particles not containing lead and at least two types of glass powder not containing lead wherein one kind of the glass powder is SiO 2. , B 2 O 3 , Al 2 O 3 , BaO, ZnO-containing Si—B—Al—Ba—Zn—O based glass powder, the total amount of the Si—B—Al—Ba—Zn—O based glass powder being 100 Si—B— containing 5% by mass to 12% by mass of B 2 O 3 with respect to mass%, and another type of glass powder containing SiO 2 , B 2 O 3 , Al 2 O 3 , and BaO.
  • the Al—Ba—O glass powder contains B 2 O 3 in an amount of 14% by mass to 25% by mass with respect to 100% by mass of the total amount of the Si—B—Al—Ba—O glass powder. It is a composition for resistors.
  • the component composition of the Si—B—Al—Ba—Zn—O-based glass powder in the first invention is such that the total amount of Si—B—Al—Ba—Zn—O-based glass powder is 100.
  • the resistance characterized by containing 4 mass% or less and 35 mass% or less of BaO by mass% or less. It is a use composition.
  • ruthenium-based conductive particles not containing lead in the first and second aspects are ruthenium oxide (RuO 2 ).
  • a fourth invention of the present invention is a composition for a resistor, characterized in that the specific surface area of ruthenium oxide (RuO 2 ) in the third invention is 5 m 2 / g or more and 150 m 2 / g or less. .
  • RuO 2 ruthenium oxide
  • the resistor composition and the organic vehicle according to the first to fourth aspects wherein the resistor composition is dispersed in the organic vehicle. It is a resistor paste.
  • the sixth invention of the present invention is a thick film resistor which is a fired body of the resistor paste according to the fifth invention formed on a ceramic substrate.
  • the resistance temperature coefficient of a thick film resistor made of ruthenium-based conductive particles not containing lead and glass powder containing no lead, which has been difficult in the past, is changed from a low resistance value region to a high resistance value region. Therefore, it is possible to easily adjust to a value close to 0 within ⁇ 100 ppm / ° C., and there is an industrially remarkable effect.
  • the present invention provides a resistor that does not contain lead and has a resistance temperature coefficient close to 0 in a wide resistance value region, which has been difficult in the past, and the present invention contains ruthenium-based conductive particles that do not contain lead, and lead.
  • the temperature coefficient of resistance of the resistor which is a fired body of the resistor composition, is within ⁇ 100 ppm / ° C by limiting the components of the glass powder. It makes use of the fact that it can be close to zero.
  • the resistor paste is generally fired at a temperature of about 800 to 900 ° C.
  • the softening point of the glass powder used as the raw material of the resistor paste needs to be lower than the firing temperature.
  • SiO 2 is used as a skeleton, and the softening point is adjusted by the type and blending amount of other metal oxides.
  • B 2 O 3 , Al 2 O 3 , BaO, ZnO or the like is used as a metal oxide other than SiO 2 .
  • lead ruthenate Pb 2 Ru 2 O 7
  • the composition of the glass powder component is important. That is, if the temperature coefficient of resistance becomes too negative, it becomes difficult to adjust to a value near 0 within ⁇ 100 ppm / ° C. even if a regulator is used, but the resistance temperature coefficient is a positive value. If it exists, it becomes possible to adjust the resistance temperature coefficient to a value near 0 within ⁇ 100 ppm / ° C. by adding a regulator.
  • the resistance temperature coefficient becomes too large on the positive side, and there is a limit to the adjustment of the resistance temperature coefficient by adding a regulator. Mixing glass components with a low coefficient is important.
  • the SiO 2 —B 2 O 3 —Al 2 O 3 system is suitable from the viewpoint of softening point and chemical stability.
  • the resistance temperature coefficient is increased on the positive side by containing a large amount of glass powder having a low content of B 2 O 3.
  • the glass powder with a high content of B 2 O 3 that has a negative temperature coefficient of resistance is often used.
  • the temperature coefficient of resistance can be made negative by containing it, and it has been found that the temperature coefficient of resistance can be adjusted to a value near 0 within ⁇ 100 ppm / ° C in a wide resistance value region. .
  • the constituent members of the present invention will be described in detail.
  • SiO 2 is a component that serves as a skeleton of one glass powder structure of the present invention, and the content thereof is preferably 20% by mass or more and 45% by mass or less with respect to 100% by mass of one glass powder.
  • the content is less than 20% by mass, chemical stability may be lowered and characteristics may vary.
  • the softening point may increase too much.
  • B 2 O 3 is also a component that becomes a skeleton of one glass powder structure of the present invention, and has an effect of lowering the softening point of glass.
  • the content is 5% by mass or more and 12% by mass or less with respect to 100% by mass of one glass powder. If the content is less than 5% by mass, the toughness of the glass is lowered and cracks are likely to occur. On the other hand, when it contains more than 12 mass%, it will be easy to raise
  • Al 2 O 3 has a function of improving the durability of one glass powder of the present invention, and its content is 5% by mass or more and 20% by mass or less with respect to 100% by mass of one glass powder. Is preferred. When the content is less than 5% by mass, phase separation of the glass tends to occur, and the durability of the glass may be lowered. If it is more than 20% by mass, the softening point may increase too much.
  • BaO has the function of lowering the softening point in one glass of the present invention that does not contain lead, and has the effect of increasing the dielectric constant and enhancing the insulation when a voltage is applied.
  • the content thereof is preferably 4% by mass or more and 35% by mass or less with respect to 100% by mass of one glass powder. If the content is less than 4% by mass, the softening point of the glass may not be lowered sufficiently. When it is more than 35% by mass, the durability of the glass may be lowered.
  • ZnO also has a function of lowering the softening point in one glass containing no lead of the present invention.
  • the content is preferably 5% by mass or more and 35% by mass or less with respect to 100% by mass of one glass powder. If the content is less than 5% by mass, the softening point of the glass may not be lowered sufficiently. When it is more than 35% by mass, the durability of the glass may be lowered.
  • the essential components of the Si—B—Al—Ba—Zn—O-based glass powder are SiO 2 , B 2 O 3 , Al 2 O 3 , BaO, and ZnO, but other components may be included.
  • CaO can be used as a component that lowers the softening point, like BaO.
  • Bi 2 O 3 the softening point of the glass can be lowered.
  • it is contained in a large amount, it becomes easy to crystallize, and various characteristics may be deteriorated, so the addition amount needs attention.
  • ZrO 2 may be contained for the purpose of enhancing the chemical stability of the glass, but if it is contained in a large amount, the softening point of the glass cannot be lowered and the softening point may become too high. .
  • Alkali metal oxides of K, Na and Li are also effective for the purpose of lowering the softening point. However, since the insulating properties of the glass are lowered and the load characteristics of the resistor are lowered, the electrical properties of the resistor are added when added. Addition within a range where there is no problem in deterioration of characteristics is desirable.
  • SiO 2 is a component that becomes the skeleton of the other glass structure of the present invention, and the content thereof is preferably 20% by mass or more and 38% by mass or less with respect to 100% by mass of the other glass powder.
  • the content is less than 20% by mass, the chemical stability is lowered.
  • the content is more than 38% by mass, the softening point may be excessively increased.
  • B 2 O 3 is also a component that becomes the skeleton of the other glass structure of the present invention, and has an effect of lowering the softening point of the glass.
  • the content is 14% by mass or more and 25% by mass or less with respect to 100% by mass of the other glass powder. When the content is less than 14% by mass, the resistance temperature coefficient of the resistor tends to be a negative value. On the other hand, when it contains more than 25 mass%, glass will melt
  • Al 2 O 3 functions to improve the durability of the other glass of the present invention, and its content is 5% by mass or more and 15% by mass or less with respect to 100% by mass of the other glass powder. Is preferred. When the content is less than 5% by mass, phase separation of the glass tends to occur, and the durability of the glass may be lowered. On the other hand, if the amount is more than 15% by mass, the softening point may increase too much.
  • BaO has a function of lowering the softening point in the other glass of the present invention that does not contain lead, and has an effect of increasing the insulation when a voltage is applied because of its high dielectric constant.
  • the content is preferably 4% by mass or more and 35% by mass or less with respect to 100% by mass of the other glass powder. When the content is less than 4% by mass, the softening point of the glass is increased, and when it is more than 35% by mass, the durability of the glass may be lowered.
  • the essential components of the Si—B—Al—Ba—O glass powder are SiO 2 , B 2 O 3 , Al 2 O 3 and BaO, but other components may be included.
  • ZnO can be used for lowering the softening point, like BaO.
  • This ZnO is an essential component in one “Si—B—Al—Ba—Zn—O-based glass powder” described above, but the other glass powder has a high B 2 O 3 content, Since the softening point can be lowered sufficiently, it is not an essential component.
  • CaO can be used as a component that lowers the softening point in the same manner as BaO.
  • the softening point of the glass can be lowered. However, if it is contained in a large amount, it becomes easy to crystallize, and various characteristics may be deteriorated. Further, ZrO 2 may be contained for the purpose of enhancing the chemical stability of the glass, but if it is contained in a large amount, the softening point of the glass cannot be lowered and the softening point may become too high. .
  • Alkali metal oxides of K, Na and Li are also effective for the purpose of lowering the softening point.
  • the electrical properties of the resistor are added when added. Addition within a range where there is no problem in deterioration of characteristics is desirable.
  • the ratio of “Si—B—Al—Ba—Zn—O-based glass powder” and “Si—B—Al—Ba—O-based glass powder” can be arbitrarily selected from the target resistance value and resistance temperature coefficient. However, the ratio of “Si—B—Al—Ba—Zn—O-based glass powder” is increased in the region where the temperature coefficient of resistance tends to be negative, and the resistance temperature coefficient is set to a positive value. In the region where the resistance value tends to be low, the ratio of “Si—B—Al—Ba—O-based glass powder” is increased.
  • the particle size of the glass powder is not particularly defined and may be selected according to the purpose of use. However, if the particle size is too large, the resistance value variation of the resistor increases or the load characteristics deteriorate, which is not preferable. In order to avoid these, the average particle size of the glass powder is preferably 3 ⁇ m or less, and more preferably 1.5 ⁇ m or less. Glass powders larger than 3 ⁇ m can be reduced in size by pulverization. For pulverization of the glass to obtain this particle size, a ball mill, a planetary mill, a bead mill, or the like can be used. In order to sharpen the particle size of the pulverized glass powder, it is preferable to use wet pulverization.
  • ruthenium-based conductive particles containing no lead are preferably ruthenium oxide.
  • the resistance temperature coefficient of a glass powder not containing lead and a resistor formed using ruthenium oxide as a conductive particle tends to be a negative value, and the resistance value is too low.
  • the ruthenium oxide used as the conductive particles preferably has a specific surface area of 5 m 2 / g or more and 150 m 2 / g or less.
  • the resistance value of the resistor is low, and the resistance temperature coefficient tends to be low when compared with the same resistance value.
  • Select the appropriate particle size according to the target resistance value it is preferable to do this.
  • conductive particles besides ruthenium oxide, bismuth ruthenate, calcium ruthenate, strontium ruthenate, barium ruthenate and the like can be used. If necessary, a mixture of two or more kinds of the above conductive particles or a conductive particle other than ruthenium can be mixed with the above conductive particles.
  • ⁇ Ratio of conductive particles to glass powder The ratio between the ruthenium-based conductive particles and the glass powder can be changed depending on the desired resistance value and the like.
  • an additive generally used for the purpose of improving or adjusting the resistance value, resistance temperature coefficient, load characteristic, trimming property of the resistor may be added.
  • Typical additives include Nb 2 O 5 , Ta 2 O 5 , TiO 2 , CuO, MnO 2 , ZrO 2 , Al 2 O 3 , SiO 2 , ZrSiO 4 and the like. By adding these additives, a resistor having more excellent characteristics can be produced.
  • the content of the additive is adjusted depending on the purpose, it is usually 10 parts by mass or less with respect to 100 parts by mass in total of the conductive particles and the glass powder.
  • Organic vehicle The conductive particles and the glass powder are mixed and dispersed in an organic vehicle in order to obtain a resistor paste for printing after adding additives as necessary.
  • the organic vehicle to be used is not particularly limited, and a solution in which a resin such as ethyl cellulose, acrylic acid ester, methacrylic acid ester, rosin, maleic acid ester is dissolved in a solvent such as terpineol, butyl carbitol, or butyl carbitol acetate is usually used. Used. Moreover, a dispersing agent, a plasticizer, etc. can be added as needed.
  • the method for dispersing the conductive particles, glass powder, additives and the like in the organic vehicle is not particularly limited, and a three-roll mill, a bead mill, a planetary mill or the like generally used for dispersing fine particles may be used. it can.
  • the content of the organic vehicle is appropriately adjusted depending on the printing and coating method, but is about 20 to 200 parts by mass with respect to 100 parts by mass in total of the conductive particles, glass powder, and additives.
  • the softening point of each glass powder was measured.
  • the softening point was measured using TG-DTA (TG / DTA320 type manufactured by Seiko Denshi Co., Ltd.), the DTA curve was measured, and the value obtained from the third inflection point of the obtained DTA curve was taken as the softening point.
  • the value of D50 by the laser diffraction type particle size distribution measurement was used for the average particle diameter of glass powder. Table 1 shows the composition, softening point, and average particle size of the glass powder subjected to this evaluation.
  • Example 1 glass powder obtained by mixing RuO 2 powder having a specific surface area of 15 m 2 / g and A-1 and B-1 was used, and in Example 2, RuO 2 powder having a specific surface area of 90 m 2 / g and A— Glass powder mixed with 2 and B-2 was used.
  • a thick film resistor was formed by firing at a peak temperature of 850 ° C. ⁇ 9 minutes for a total of 30 minutes.
  • the thick film resistor had a resistor width of 1.0 mm and a resistor length (between electrodes) of 1.0 mm. Five such substrates were prepared under the same conditions for each sample.
  • the film thickness and the resistance value are measured, respectively, the converted area resistance value when the film thickness is 7 ⁇ m, the temperature coefficient of resistance from 25 ° C. to ⁇ 55 ° C. (Cold-TCR: below) C-TCR), a temperature coefficient of resistance (HOT-TCR: hereinafter referred to as H-TCR) from 25 ° C. to 125 ° C. was calculated.
  • the film thickness is obtained by extracting one arbitrary alumina substrate, measuring the thickness of five thick film resistors formed on the alumina substrate with a stylus type thickness roughness meter, and calculating the average value. The “measured film thickness” of the entire sample was used.
  • the area resistance value was calculated from the average value of the measured resistance values of five thick film resistors formed on five alumina substrates, a total of 25 thick film resistors, and the above “measured film thickness”. The value was recalculated and evaluated by the “converted area resistance value” when the film thickness was 7 ⁇ m. The calculation was performed using the following formula (1), where the average value of the measured values obtained by measuring the resistance values of the 25 thick film resistors by the four-terminal method was “measured resistance value”. In this evaluation, “7 ⁇ m” was used as the “equivalent film thickness”.
  • the temperature coefficient of resistance is determined when the resistance value is measured after holding the thick film resistor at ⁇ 55 ° C., 25 ° C., and 125 ° C. for 15 minutes, and the respective resistance values are R ⁇ 55 , R 25 , and R 125.
  • the average values of the values calculated from the five thick film resistors were used, which were values calculated by the following formulas (2) and (3).
  • the converted film thickness resistance value and the resistance temperature coefficient (C-TCR, H-TCR) value, the specific surface area of RuO 2 used for each sample, and the resistor paste preparation Table 2 shows the content of the resistor composition.
  • Example 1 and Comparative Examples 1 and 2 ruthenium oxide particles having a specific surface area of 15 m 2 / g were used.
  • Example 1 Si—B—Al—Ba—Zn— Both the O-type glass powder “A-1” and the Si—B—Al—Ba—O-type glass powder “B-1” were used.
  • Comparative Examples 1 and 2 only one type of glass powder was used. Is used.
  • the resistance temperature coefficient is too large to be 581 ppm / ° C. or more in an “area where the resistance value is low” where the sheet resistance value is 1.1 k ⁇ / ⁇ or less, and even if a regulator is used, ⁇ 100 ppm. It turns out that it is difficult to set to / °C.
  • the resistance temperature coefficient becomes a negative value of ⁇ 175 ppm / ° C. or less in the “region where the resistance value is relatively high” having an area resistance value of 0.95 k ⁇ / ⁇ or more, and is ⁇ 100 ppm / ° C. I can't do anything.
  • the temperature coefficient of resistance is in the range of 52 to 201 ppm / ° C. in the area resistance value region of 0.087 k ⁇ / ⁇ to 110 k ⁇ / ⁇ , and a regulator such as manganese oxide, niobium oxide, titanium oxide, or the like. It can be seen that it can be easily adjusted to ⁇ 100 ppm / ° C. by adding.
  • Example 2 In Example 2 and Comparative Examples 3 and 4, ruthenium oxide particles having a specific surface area of 90 m 2 / g were used.
  • Example 2 the Si—B—Al—Ba—Zn—O-based glass powder “A-2” was used.
  • the resistance temperature coefficient is too high at 599 ppm / ° C. or more in the “resistance low region” where the sheet resistance value is 1 k ⁇ / ⁇ or less, and even if a regulator is used, ⁇ 100 ppm / ° C. It turns out that it is difficult to do. Further, in Comparative Example 4, the resistance temperature coefficient becomes a negative value of ⁇ 250 ppm / ° C. or less in the “region where the resistance value is relatively high” having an area resistance value of 1 k ⁇ / ⁇ or more, and is set to ⁇ 100 ppm / ° C. I can't.
  • the temperature coefficient of resistance is in the range of 21 to 145 ppm / ° C. in the area resistance value region of 0.085 k ⁇ / ⁇ to 110 k ⁇ / ⁇ , and adjustment of manganese oxide, niobium oxide, titanium oxide, etc. It can be seen that it can be easily adjusted to ⁇ 100 ppm / ° C. by adding an agent.
  • the temperature coefficient of resistance of the thick film resistor using ruthenium-based conductive particles and glass powder as raw materials is low. It can be seen that the adjustment can be easily made within ⁇ 100 ppm / ° C. from the resistance value region to the high resistance value region.

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Abstract

The present invention provides: a resistor composition and a resistor paste that contain no lead component and exhibit excellent characteristics of having a near-zero resistance temperature coefficient falling within the range of ±100 ppm/°C; and a thick-film resistor using such a resistor composition or a resistor paste. The resistor composition according to the present invention comprises, as major constituents, lead-free ruthenium-based conductive particles and at least two types of lead-free glass powders, the resistor composition being characterized in that: one of the glass powders is a Si-B-Al-Ba-Zn-O-based glass powder that includes SiO2, B2O3, Al2O3, BaO, and ZnO, and contains 5-12 mass% of B2O3; and another type of the glass powders is a Si-B-Al-Ba-O-based glass powder that includes SiO2, B2O3, Al2O3, and BaO, and contains 14-25 mass% of B2O3.

Description

抵抗体用組成物及びこれを含んだ抵抗体ペーストとそれを用いた厚膜抵抗体Resistor composition, resistor paste containing the same, and thick film resistor using the same
　本発明は、チップ抵抗器、ハイブリットＩＣ、または、抵抗ネットワーク等の電子部品の製造に用いられる抵抗体を形成するための抵抗体ペーストと、その抵抗体ペーストを構成する抵抗体用組成物、及び、その抵抗体ペーストを用いて形成した厚膜抵抗体に関する。 The present invention relates to a resistor paste for forming a resistor used for manufacturing an electronic component such as a chip resistor, a hybrid IC, or a resistor network, a resistor composition that constitutes the resistor paste, and And a thick film resistor formed using the resistor paste.
　一般に、チップ抵抗器、ハイブリットＩＣ、又は、抵抗ネットワーク等の電子部品の製造に用いられる厚膜抵抗体は、セラミック基板に抵抗体ペーストを印刷、焼成する事によって形成されている。この厚膜抵抗体の形成に用いられる組成物は、導電粒子として酸化ルテニウムを代表とするルテニウム系導電粒子とガラス粉末を主な成分としたものが広く用いられている。なお、厚膜抵抗体とは、前述の様に抵抗体ペーストを用いて、印刷、焼成して得られる比較的厚みのある抵抗体のことであり、スパッタリング又は真空蒸着により形成される非常に薄い薄膜抵抗体と区別して用いられる一般的な名称である。
　このルテニウム系導電粒子とガラス粉末が厚膜抵抗体用の組成物に広く用いられる理由は、空気中での焼成ができ、抵抗温度係数（ＴＣＲ）を０に近づける事が可能である事に加え、広い領域の抵抗値の抵抗体が形成可能である事などが挙げられる。 Generally, a thick film resistor used for manufacturing an electronic component such as a chip resistor, a hybrid IC, or a resistor network is formed by printing and baking a resistor paste on a ceramic substrate. As the composition used for forming this thick film resistor, a composition mainly composed of ruthenium-based conductive particles represented by ruthenium oxide and glass powder as conductive particles is widely used. The thick film resistor is a relatively thick resistor obtained by printing and baking using a resistor paste as described above, and is very thin formed by sputtering or vacuum evaporation. It is a general name used in distinction from thin film resistors.
The reason why these ruthenium-based conductive particles and glass powder are widely used in the composition for thick film resistors is that they can be fired in air and the resistance temperature coefficient (TCR) can be brought close to zero. In other words, it is possible to form a resistor having a wide range of resistance values.
　このようなルテニウム系導電粒子とガラス粉末からなる抵抗体用組成物は、その配合比によって抵抗値を変える事ができる。即ち、ルテニウム系導電粒子の配合比を多くすると抵抗値が下がり、ルテニウム系導電粒子の配合比を少なくすると抵抗値が上がる。この事を利用して、厚膜抵抗体では、ルテニウム系導電粒子とガラス粉末の配合比を調整して所望する抵抗値を出現させている。 The resistance composition of such a ruthenium-based conductive particle and glass powder can change the resistance value depending on its blending ratio. That is, when the mixing ratio of the ruthenium-based conductive particles is increased, the resistance value is decreased, and when the mixing ratio of the ruthenium-based conductive particles is decreased, the resistance value is increased. By utilizing this fact, in the thick film resistor, a desired resistance value appears by adjusting the mixing ratio of the ruthenium-based conductive particles and the glass powder.
　従来、厚膜抵抗体にもっとも多く使用されているルテニウム系導電粒子としては、ルチル型の結晶構造を有する酸化ルテニウム（ＲｕＯ2）、パイロクロア型の結晶構造を有するルテニウム酸鉛（Ｐｂ2Ｒｕ2Ｏ7）があげられる。これらはいずれも金属的な導電性を示す酸化物である。 Conventionally, ruthenium-based conductive particles most frequently used in thick film resistors include ruthenium oxide (RuO 2 ) having a rutile crystal structure and lead ruthenate (Pb 2 Ru 2 O having a pyrochlore crystal structure). 7 ). These are all oxides showing metallic conductivity.
　一方、厚膜抵抗体に使用されるガラス粉末には、一般的に抵抗体ペーストの焼成温度よりも低い軟化点のガラスが用いられており、従来は酸化鉛（ＰｂＯ）を含むガラス粉末が多く用いられていた。その理由としては、ＰｂＯにはガラス粉末の軟化点を下げる効果があるため、含有率を変える事によって広範囲に渡り厚膜抵抗体に適した軟化点に容易に変更できる事、またＰｂＯを含有させる事により、比較的化学的な耐久性が高いガラス粉末が作れる事、絶縁性が高く耐圧性に優れる事が挙げられる。 On the other hand, the glass powder used for the thick film resistor is generally a glass having a softening point lower than the firing temperature of the resistor paste. Conventionally, many glass powders containing lead oxide (PbO) are used. It was used. The reason for this is that PbO has the effect of lowering the softening point of the glass powder, so it can be easily changed to a softening point suitable for thick film resistors over a wide range by changing the content rate, and PbO is contained. This makes it possible to produce glass powder with relatively high chemical durability, and high insulation and excellent pressure resistance.
　ところで、ルテニウム系導電粒子とガラス粉末からなる抵抗体用組成物では、低い抵抗値が望まれる場合にはルテニウム系導電粒子を多く、ガラス粉末を少なく配合し、高い抵抗値が望まれる場合にはルテニウム系導電粒子を少なく、ガラス粉末を多く配合して抵抗値を調整している。この時、ルテニウム系導電粒子を多く配合する低い抵抗値領域では抵抗温度係数が大きく正の値になりやすく、ルテニウム系導電粒子の配合が少ない高い抵抗値領域では抵抗温度係数が負の値になりやすい特徴がある。
　なお、抵抗温度係数とは、温度変化に対する抵抗値の変化の割合を表したもので、抵抗体の重要な特性の一つである。 By the way, in the composition for a resistor composed of ruthenium-based conductive particles and glass powder, when a low resistance value is desired, a large amount of ruthenium-based conductive particles and a small amount of glass powder are blended, and when a high resistance value is desired. The resistance value is adjusted by blending a large amount of glass powder with few ruthenium-based conductive particles. At this time, the resistance temperature coefficient tends to be a large positive value in the low resistance region where many ruthenium-based conductive particles are blended, and the resistance temperature coefficient becomes negative in the high resistance region where there are few ruthenium-based conductive particles blended. There are easy features.
The temperature coefficient of resistance represents the rate of change of the resistance value with respect to the temperature change, and is one of the important characteristics of the resistor.
　一般的に各種電子部品は動作中に発熱するが、発熱により抵抗値が変化してしまうと電子部品の動作が変化してしまうため、０に近い抵抗温度係数が求められる場合が多い。
　この抵抗温度係数は、調整剤と呼ばれる主に金属酸化物からなる添加物を、抵抗体用組成物に加える事で調整が可能である。この調整の内、温度係数を負側に調整する事は比較的容易であり、そのような調整剤としてはマンガン酸化物、ニオブ酸化物、チタン酸化物等が挙げられる。
　しかし、抵抗温度係数を正の値に調整する調整剤はほとんど無く、負の値の抵抗温度係数を有する抵抗体用組成物の抵抗温度係数を０付近に調整する事は実質上行えなかった。
　したがって、抵抗温度係数が負になりやすい高い抵抗値領域において、抵抗温度係数が正の値になる、導電粒子とガラス粉末の組み合わせの利用が必要であった。
　その様な組み合わせとして利用されるルテニウム酸鉛（Ｐｂ2Ｒｕ2Ｏ7）は酸化ルテニウム（ＲｕＯ2）よりも比抵抗が高く、厚膜抵抗体を形成した時の抵抗温度係数が高く正の値になる特徴がある。このため、高い抵抗値領域では導電粒子としてルテニウム酸鉛（Ｐｂ2Ｒｕ2Ｏ7）が多く使用されてきた。 In general, various electronic components generate heat during operation, but if the resistance value changes due to heat generation, the operation of the electronic component changes, so a resistance temperature coefficient close to 0 is often required.
This resistance temperature coefficient can be adjusted by adding an additive mainly made of a metal oxide called a modifier to the resistor composition. Of these adjustments, it is relatively easy to adjust the temperature coefficient to the negative side, and examples of such adjusting agents include manganese oxide, niobium oxide, and titanium oxide.
However, there is almost no regulator that adjusts the resistance temperature coefficient to a positive value, and it has been impossible to adjust the resistance temperature coefficient of a resistor composition having a negative resistance temperature coefficient to near zero.
Therefore, it is necessary to use a combination of conductive particles and glass powder that has a positive resistance temperature coefficient in a high resistance value region where the resistance temperature coefficient tends to be negative.
Lead ruthenate (Pb 2 Ru 2 O 7 ) used as such a combination has a higher specific resistance than ruthenium oxide (RuO 2 ), and has a high resistance temperature coefficient and a positive value when a thick film resistor is formed. There is a feature to become. For this reason, lead ruthenate (Pb 2 Ru 2 O 7 ) has often been used as conductive particles in the high resistance region.
　このように、特に高い抵抗値領域の従来の抵抗体用組成物には、導電粒子及びガラス粉末の両方に鉛成分を含有した材料が用いられていた。
　しかしながら、鉛成分は人体への影響および公害の点から望ましくなく、ＲｏＨＳ指令などで規制対象物質となっており、鉛を含有しない抵抗体用組成物の開発が強く求められている。 Thus, a material containing a lead component in both conductive particles and glass powder has been used in a conventional resistor composition having a particularly high resistance value region.
However, the lead component is undesirable from the viewpoint of influence on the human body and pollution, and is a regulated substance under the RoHS directive and the like, and there is a strong demand for the development of a resistor composition that does not contain lead.
　そのような抵抗体用組成物として特許文献１では、ルテニウム系導電粒子としてルテニウム酸カルシウム、ルテニウム酸ストロンチウム、ルテニウム酸バリウムを抵抗体用組成物に用いた抵抗体ペーストが開示され、その特徴として、平均粒径が５μｍ以上５０μｍ以下である導電粒子が用いられている。
　しかしながら、通常、粒径の大きい導電粒子を用いると、その形成された抵抗体は電流ノイズが大きく、良好な負荷特性を得る事ができない場合があり、特許文献１に記載の粒径ではノイズを低く抑える事が困難である、という課題を抱えている。 Patent Document 1 discloses a resistor paste using calcium ruthenate, strontium ruthenate, and barium ruthenate as a ruthenium-based conductive particle as a resistor composition. Conductive particles having an average particle diameter of 5 μm or more and 50 μm or less are used.
However, usually, when conductive particles having a large particle size are used, the formed resistor has a large current noise, and it may not be possible to obtain good load characteristics. It has a problem that it is difficult to keep it low.
　特許文献２には、酸化ルテニウムを溶解させたガラスを用いる事によって鉛を含有しないルテニウム系導電粒子の分解を抑制する方法が提案されている。
　しかし、ガラス粉末中に溶解する酸化ルテニウムの量は、製造条件のばらつきによって大きく影響され変動が大きいため、抵抗値が安定しないという課題がある。 Patent Document 2 proposes a method for suppressing decomposition of ruthenium-based conductive particles not containing lead by using glass in which ruthenium oxide is dissolved.
However, since the amount of ruthenium oxide dissolved in the glass powder is greatly affected by variations in manufacturing conditions and greatly fluctuates, there is a problem that the resistance value is not stable.
　特許文献３では、ルテニウム系導電粒子としてルテニウム酸ビスマスとビスマスを含有するガラスとの抵抗体用組成物が開示されているが、この組み合わせで形成された抵抗体の抵抗温度係数は負の値に大きくなってしまうため、抵抗温度係数を±１００ｐｐｍ／℃以内の０に近い値にする事ができない。 Patent Document 3 discloses a resistor composition of bismuth ruthenate and glass containing bismuth as ruthenium-based conductive particles, but the resistance temperature coefficient of the resistor formed by this combination has a negative value. Therefore, the temperature coefficient of resistance cannot be set to a value close to 0 within ± 100 ppm / ° C.
　特許文献４では、ガラス粉末の塩基度をルテニウム複合酸化物の塩基度に近づけ、さらにガラス中に結晶相を析出させる事によってルテニウム複合酸化物の酸化ルテニウムへの分解を抑制する方法が提案されている。この方法では、厚膜抵抗体中にＭＳｉ2Ａｌ2Ｏ8結晶（Ｍ：Ｂａ及び／又はＳｒ）が存在する事を特徴としているが、この様な結晶を均一に分散させる事は困難であり、抵抗値が安定しない場合がある。 Patent Document 4 proposes a method of suppressing the decomposition of ruthenium composite oxide into ruthenium oxide by bringing the basicity of glass powder close to the basicity of ruthenium composite oxide and further precipitating a crystal phase in the glass. Yes. This method is characterized by the presence of MSi 2 Al 2 O 8 crystals (M: Ba and / or Sr) in the thick film resistor, but it is difficult to uniformly disperse such crystals. The resistance value may not be stable.
　さらに、特許文献５には、酸化ルテニウムとＳｉＯ2－Ｂ2Ｏ3－Ｋ2Ｏガラス粉末を含む厚膜抵抗体が開示され、この厚膜抵抗体は、その抵抗温度係数が負の値にはならないと記載されている。
　しかし、ガラス組成中に１重量部以上のアルカリ金属酸化物を含有させているため、ガラスの絶縁性が低下し、抵抗体の負荷特性が低下する恐れがある。 Further, Patent Document 5 discloses a thick film resistor containing ruthenium oxide and SiO 2 —B 2 O 3 —K 2 O glass powder. The thick film resistor has a negative resistance temperature coefficient. It is stated that it should not.
However, since 1 part by weight or more of the alkali metal oxide is contained in the glass composition, the insulating property of the glass is lowered, and the load characteristics of the resistor may be lowered.
　以上のように、ルテニウム系導電粒子とガラス粉末からなる抵抗体用組成物では、ルテニウム系導電粒子を多く配合する低い抵抗値領域では抵抗温度係数が正の値に大きくなりやすく、ルテニウム系導電粒子の配合が少ない高い抵抗値領域では抵抗温度係数が負の値になりやすい特徴がある。そこで、主に金属酸化物からなる調整剤を抵抗体用組成物に加える事で、抵抗温度係数を調整する事が行われているが、負の値の抵抗温度係数を、正側に調整する調整剤はほとんど無く、非常に困難である。また、非常に大きい正の値を示す抵抗温度係数を負方向に調整し、±１００ｐｐｍ／℃以内と０に近づける様に調整する事も難しい。 As described above, in the resistor composition composed of the ruthenium-based conductive particles and the glass powder, the resistance temperature coefficient tends to increase to a positive value in the low resistance value region in which many ruthenium-based conductive particles are blended, and the ruthenium-based conductive particles. In a high resistance value region where the amount of blending is small, the temperature coefficient of resistance tends to be negative. Therefore, the temperature coefficient of resistance is adjusted by adding a regulator mainly composed of a metal oxide to the resistor composition, but the resistance temperature coefficient of a negative value is adjusted to the positive side. There are few modifiers and it is very difficult. It is also difficult to adjust the temperature coefficient of resistance, which shows a very large positive value, in the negative direction so as to be close to 0 within ± 100 ppm / ° C.
　従来、用いられてきたＰｂＯを含むガラス粉末とルテニウム系導電粒子による抵抗体用組成物では抵抗温度係数を調整する調整剤の効果が大きく、抵抗温度係数を調整できる範囲も広かったが、鉛を含まないガラス粉末では調整剤の効果が小さく、抵抗温度係数を調整できる範囲が狭くなってしまっている。そのため、広い抵抗値領域において、鉛を含有しないガラス粉末とルテニウム系導電粒子の組み合わせにおいて、調整剤を用いて抵抗温度係数を±１００ｐｐｍ／℃以内の０に近い値にする事ができる組合せにする必要がある。 Conventionally, a resistor composition comprising a glass powder containing PbO and ruthenium-based conductive particles that has been used has a large effect of a regulator that adjusts the resistance temperature coefficient, and the range in which the resistance temperature coefficient can be adjusted is wide. When the glass powder is not included, the effect of the adjusting agent is small, and the range in which the temperature coefficient of resistance can be adjusted is narrowed. Therefore, in a wide resistance value range, in a combination of glass powder not containing lead and ruthenium-based conductive particles, the temperature coefficient of resistance can be made a value close to 0 within ± 100 ppm / ° C. using a regulator. There is a need.
特開２００５－１２９８０６号公報Japanese Patent Laid-Open No. 2005-129806 特開２００３－７５１７号公報JP 2003-7517 A 特開平８－２５３３４２号公報JP-A-8-253342 特開２００７－１０３５９４号公報JP 2007-103594 A 特開２００１－１９６２０１号公報Japanese Patent Laid-Open No. 2001-196201
　上述のように、鉛を含まない導電粒子とガラス粉末を用いた試みが成されて、様々な抵抗体ペーストが開示されているが、まだ実用化の面で十分に満足できる特性を有する抵抗体ペーストは量産化されていない。
　そこで、本発明は、このような状況に鑑みなされたものであり、鉛成分を含有せずに、抵抗温度係数が±１００ｐｐｍ／℃以内の０に近い、優れた特性を有する厚膜抵抗体を形成するための抵抗体用組成物、抵抗体ペーストを提供し、さらにそれらを用いた厚膜抵抗体の提供を目的とするものである。 As described above, attempts have been made to use lead-free conductive particles and glass powder, and various resistor pastes have been disclosed, but the resistors still have satisfactory characteristics in terms of practical use. The paste has not been mass-produced.
Therefore, the present invention has been made in view of such a situation, and a thick film resistor having excellent characteristics without containing a lead component and having a resistance temperature coefficient close to 0 within ± 100 ppm / ° C. An object of the present invention is to provide a resistor composition and a resistor paste to be formed, and to provide a thick film resistor using them.
　目的を達成するため、本発明者は鋭意研究を重ねた結果、鉛を含有しないルテニウム系導電粒子と、少なくとも２種類の鉛を含有しないガラス粉末を主な構成成分とする抵抗体用組成物において、一方のガラス粉末が、ＳｉＯ2、Ｂ2Ｏ3、Ａｌ2Ｏ3、ＢａＯ、ＺｎＯを含むＳｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系ガラス粉末で、そのガラス成分に前記Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系ガラス粉末の総量１００質量％に対し、５質量％以上、１２質量％以下のＢ2Ｏ3を含有し、他方のガラス粉末がＳｉＯ2、Ｂ2Ｏ3、Ａｌ2Ｏ3、ＢａＯを含むＳｉ－Ｂ－Ａｌ－Ｂａ－Ｏ系ガラス粉末で、そのガラス成分に前記Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｏ系ガラス粉末の総量１００質量％に対し、１４質量％以上、２５質量％以下のＢ2Ｏ3を含有する事によって、鉛成分を含有せずに抵抗温度係数が±１００ｐｐｍ／℃以内の０に近い優れた特性を有する厚膜抵抗体、及びその抵抗体を形成するための抵抗体用組成物、抵抗体ペーストが得られる事を見出し、本発明に至ったものである。 In order to achieve the object, the present inventor has conducted extensive research, and as a result, in a resistor composition comprising, as main components, ruthenium-based conductive particles containing no lead and at least two types of glass powder containing no lead. One glass powder is a Si—B—Al—Ba—Zn—O-based glass powder containing SiO 2 , B 2 O 3 , Al 2 O 3 , BaO, ZnO, and the glass component includes the Si—B— 5% by mass or more and 12% by mass or less of B 2 O 3 is contained with respect to 100% by mass of the total amount of the Al—Ba—Zn—O-based glass powder, and the other glass powder is SiO 2 , B 2 O 3 , Al Si-B-Al-Ba-O-based glass powder containing 2 O 3 and BaO, whose glass component is 14% by mass or more with respect to 100% by mass of the total amount of the Si-B-Al-Ba-O-based glass powder. And containing 25% by mass or less of B 2 O 3 Accordingly, a thick film resistor having excellent characteristics close to 0 having a resistance temperature coefficient within ± 100 ppm / ° C. without containing a lead component, and a resistor composition and a resistor paste for forming the resistor It has been found that can be obtained, and the present invention has been achieved.
　本発明の第１の発明は、鉛を含有しないルテニウム系導電粒子と、少なくとも２種類の、鉛を含有しないガラス粉末を含む抵抗体用組成物であって、そのガラス粉末の一種が、ＳｉＯ2、Ｂ2Ｏ3、Ａｌ2Ｏ3、ＢａＯ、ＺｎＯを含むＳｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系ガラス粉末で、前記Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系ガラス粉末の総量１００質量％に対し、Ｂ2Ｏ3を５質量％以上、１２質量％以下含有し、ガラス粉末の他の一種が、ＳｉＯ2、Ｂ2Ｏ3、Ａｌ2Ｏ3、ＢａＯを含むＳｉ－Ｂ－Ａｌ－Ｂａ－Ｏ系ガラス粉末で、前記Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｏ系ガラス粉末の総量１００質量％に対し、Ｂ2Ｏ3を１４質量％以上、２５質量％以下含有する事を特徴とする抵抗体用組成物である。 The first invention of the present invention is a resistor composition comprising ruthenium-based conductive particles not containing lead and at least two types of glass powder not containing lead, wherein one kind of the glass powder is SiO 2. , B 2 O 3 , Al 2 O 3 , BaO, ZnO-containing Si—B—Al—Ba—Zn—O based glass powder, the total amount of the Si—B—Al—Ba—Zn—O based glass powder being 100 Si—B— containing 5% by mass to 12% by mass of B 2 O 3 with respect to mass%, and another type of glass powder containing SiO 2 , B 2 O 3 , Al 2 O 3 , and BaO. The Al—Ba—O glass powder contains B 2 O 3 in an amount of 14% by mass to 25% by mass with respect to 100% by mass of the total amount of the Si—B—Al—Ba—O glass powder. It is a composition for resistors.
　本発明の第２の発明は、第１の発明におけるＳｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系ガラス粉末の成分組成が、Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系ガラス粉末の総量１００質量％に対し、ＳｉＯ2を２０質量％以上、４５質量％以下、Ｂ2Ｏ3を５質量％以上、１２質量％以下、Ａｌ2Ｏ3を５質量％以上、２０質量％以下、ＢａＯを４質量％以上、３５質量％以下、ＺｎＯを５質量％以上、３５質量％以下含有し、Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｏ系ガラス粉末の成分組成が、Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｏ系ガラス粉末の総量１００質量％に対し、ＳｉＯ2を２０質量％以上、３８質量％以下、Ｂ2Ｏ3を１４質量％以上、２５質量％以下、Ａｌ2Ｏ3を５質量％以上、１５質量％以下、ＢａＯを４質量％以上、３５質量％以下含有する事を特徴とする抵抗体用組成物である。 In the second invention of the present invention, the component composition of the Si—B—Al—Ba—Zn—O-based glass powder in the first invention is such that the total amount of Si—B—Al—Ba—Zn—O-based glass powder is 100. to mass%, the SiO 2 20 wt% or more, 45 wt% or less, B 2 O 3 of 5 wt% or more, 12 wt% or less, Al 2 O 3 of 5 wt% or more, 20 wt% or less of BaO 4% by mass or more and 35% by mass or less, ZnO 5% by mass or more and 35% by mass or less, and the component composition of the Si—B—Al—Ba—O-based glass powder is Si—B—Al—Ba—O. the total amount 100 mass% of the system glass powder, a SiO 2 20 wt% or more, 38 wt% or less, B 2 O 3 of 14 wt% or more, 25 wt% or less, Al 2 O 3 of 5 wt% or more, 15 The resistance characterized by containing 4 mass% or less and 35 mass% or less of BaO by mass% or less. It is a use composition.
　本発明の第３の発明は、第１及び第２の発明における鉛を含有しないルテニウム系導電粒子が、酸化ルテニウム（ＲｕＯ2）である事を特徴とする抵抗体用組成物である。 According to a third aspect of the present invention, there is provided a resistor composition, wherein the ruthenium-based conductive particles not containing lead in the first and second aspects are ruthenium oxide (RuO 2 ).
　本発明の第４の発明は、第３の発明における酸化ルテニウム（ＲｕＯ2）の比表面積が、５ｍ2／ｇ以上、１５０ｍ2／ｇ以下である事を特徴とする抵抗体用組成物である。 A fourth invention of the present invention is a composition for a resistor, characterized in that the specific surface area of ruthenium oxide (RuO 2 ) in the third invention is 5 m 2 / g or more and 150 m 2 / g or less. .
　本発明の第５の発明は、第１から第４の発明における抵抗体用組成物と有機ビヒクルを含み、前記抵抗体用組成物が、有機ビヒクル中に分散して含有している事を特徴とする抵抗体ペーストである。 According to a fifth aspect of the present invention, there is provided the resistor composition and the organic vehicle according to the first to fourth aspects, wherein the resistor composition is dispersed in the organic vehicle. It is a resistor paste.
　本発明の第６の発明は、セラミック基板上に形成された、第５の発明における抵抗体ペーストの焼成体である事を特徴とする厚膜抵抗体である。 The sixth invention of the present invention is a thick film resistor which is a fired body of the resistor paste according to the fifth invention formed on a ceramic substrate.
　本発明によれば、従来困難であった鉛を含有しないルテニウム系導電粒子と、鉛を含有しないガラス粉末を原料とする厚膜抵抗体の抵抗温度係数を、低い抵抗値領域から高い抵抗値領域に渡って、±１００ｐｐｍ／℃以内の０に近い値に容易に調整する事が可能となり、工業上顕著な効果を奏するものである。 According to the present invention, the resistance temperature coefficient of a thick film resistor made of ruthenium-based conductive particles not containing lead and glass powder containing no lead, which has been difficult in the past, is changed from a low resistance value region to a high resistance value region. Therefore, it is possible to easily adjust to a value close to 0 within ± 100 ppm / ° C., and there is an industrially remarkable effect.
　本発明は、従来では困難であった広い抵抗値領域で抵抗温度係数が０に近い鉛を含有しない抵抗体を提供するもので、本発明は鉛を含有しないルテニウム系導電粒子と、鉛を含有しないガラス粉末を主な構成成分とする抵抗体用組成物において、ガラス粉末の成分を限定する事によって、この抵抗体用組成物の焼成体である抵抗体の抵抗温度係数を±１００ｐｐｍ／℃以内の０に近づける事が可能となる事を利用している。 The present invention provides a resistor that does not contain lead and has a resistance temperature coefficient close to 0 in a wide resistance value region, which has been difficult in the past, and the present invention contains ruthenium-based conductive particles that do not contain lead, and lead. In the resistor composition comprising glass powder as the main component, the temperature coefficient of resistance of the resistor, which is a fired body of the resistor composition, is within ± 100 ppm / ° C by limiting the components of the glass powder. It makes use of the fact that it can be close to zero.
　実施例の説明に先立ち、本発明の構成について説明する。
　抵抗体ペーストは、一般に８００～９００℃前後の温度で焼成される。抵抗体ペーストの原料として使用されるガラス粉末の軟化点は、一般に焼成温度よりも低くする必要がある。鉛を含有しないガラス粉末ではＳｉＯ2を骨格とし、それ以外の金属酸化物の種類と配合量によって軟化点を調整する。本発明においては、ＳｉＯ2以外の金属酸化物として、Ｂ2Ｏ3、Ａｌ2Ｏ3、ＢａＯ、ＺｎＯ等を用いる。
　これらの成分の配合比を様々に変化させたガラス粉末とルテニウム系導電粒子からなる抵抗体用組成物を焼成して形成した抵抗体の特性を評価した結果、一定範囲内のガラス粉末成分によって、抵抗体の抵抗温度係数に傾向がある事を見出だした。
　即ち、ガラス成分中のＢ2Ｏ3の含有率が高いと抵抗体の抵抗温度係数が負の値になりやすく、Ｂ2Ｏ3の含有率が低いと抵抗体の抵抗温度係数が正の値になりやすい事を見出した。 Prior to the description of the embodiments, the configuration of the present invention will be described.
The resistor paste is generally fired at a temperature of about 800 to 900 ° C. Generally, the softening point of the glass powder used as the raw material of the resistor paste needs to be lower than the firing temperature. In the glass powder not containing lead, SiO 2 is used as a skeleton, and the softening point is adjusted by the type and blending amount of other metal oxides. In the present invention, B 2 O 3 , Al 2 O 3 , BaO, ZnO or the like is used as a metal oxide other than SiO 2 .
As a result of evaluating the characteristics of a resistor formed by firing a composition for a resistor composed of glass powder and ruthenium-based conductive particles in which the blending ratio of these components was varied, depending on the glass powder component within a certain range, It was found that the temperature coefficient of resistance of the resistor has a tendency.
That is, if the B 2 O 3 content in the glass component is high, the resistance temperature coefficient of the resistor tends to be negative, and if the B 2 O 3 content is low, the resistance temperature coefficient of the resistor is positive. I found that it is easy to become.
　鉛を含有しない抵抗体用組成物では、抵抗体の抵抗温度係数を大きな正の値にさせる導電粒子であるルテニウム酸鉛（Ｐｂ2Ｒｕ2Ｏ7）を用いる事が出来ない。その他のルテニウム系導電粒子は抵抗温度係数を大きな正の値にする事ができないため、ガラス粉末成分の配合は重要である。即ち、抵抗温度係数が負の値になり過ぎてしまうと、調整剤を用いても±１００ｐｐｍ／℃以内の０付近の値に調整する事が困難となるが、抵抗温度係数が正の値であれば、調整剤の添加によって、抵抗温度係数を±１００ｐｐｍ／℃以内の０付近の値に調整する事が可能となる。 In a resistor composition that does not contain lead, it is not possible to use lead ruthenate (Pb 2 Ru 2 O 7 ), which is a conductive particle that makes the resistance temperature coefficient of the resistor a large positive value. Since other ruthenium-based conductive particles cannot have a large positive temperature coefficient of resistance, the composition of the glass powder component is important. That is, if the temperature coefficient of resistance becomes too negative, it becomes difficult to adjust to a value near 0 within ± 100 ppm / ° C. even if a regulator is used, but the resistance temperature coefficient is a positive value. If it exists, it becomes possible to adjust the resistance temperature coefficient to a value near 0 within ± 100 ppm / ° C. by adding a regulator.
　また、ルテニウム系導電粒子を多く含有させる必要がある抵抗値が低い領域では、抵抗温度係数が正側に大きくなり過ぎ、調整剤の添加による抵抗温度係数の調整にも限界があるため、抵抗温度係数が低いガラス成分の配合は重要となる。 Also, in the low resistance region where it is necessary to contain a large amount of ruthenium-based conductive particles, the resistance temperature coefficient becomes too large on the positive side, and there is a limit to the adjustment of the resistance temperature coefficient by adding a regulator. Mixing glass components with a low coefficient is important.
　鉛を含有しないガラス粉末の成分としては、ＳｉＯ2－Ｂ2Ｏ3－Ａｌ2Ｏ3系が軟化点や化学的安定性の点から適している。
　本発明ではルテニウム系導電粒子の含有が少なく抵抗温度係数が負の値になりやすい高い抵抗値領域では、Ｂ2Ｏ3の含有率が低いガラス粉末を多く含有させる事により抵抗温度係数を正側に大きくする事ができ、ルテニウム系導電粒子の含有が多く抵抗温度係数がプラスになりやすい高い抵抗値領域では、抵抗温度係数が負側になるＢ2Ｏ3の含有率が高いガラス粉末を多く含有させる事により抵抗温度係数を負側にする事ができる事を見出し、広い抵抗値領域で抵抗温度係数を±１００ｐｐｍ／℃以内の０付近の値に調整する事が可能となる事を見出した。
　以下、本発明の構成部材について詳しく説明する。 As a component of glass powder not containing lead, the SiO 2 —B 2 O 3 —Al 2 O 3 system is suitable from the viewpoint of softening point and chemical stability.
In the present invention, in a high resistance region where the content of ruthenium-based conductive particles is small and the resistance temperature coefficient tends to be negative, the resistance temperature coefficient is increased on the positive side by containing a large amount of glass powder having a low content of B 2 O 3. In a high resistance region where the content of ruthenium-based conductive particles is large and the temperature coefficient of resistance tends to be positive, the glass powder with a high content of B 2 O 3 that has a negative temperature coefficient of resistance is often used. It was found that the temperature coefficient of resistance can be made negative by containing it, and it has been found that the temperature coefficient of resistance can be adjusted to a value near 0 within ± 100 ppm / ° C in a wide resistance value region. .
Hereinafter, the constituent members of the present invention will be described in detail.
［本発明のＳｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系ガラス粉末の成分組成］
　本発明の一方のガラス粉末の組成について詳細に説明する。
＜ＳｉＯ2＞
　ＳｉＯ2は本発明の一方のガラス粉末構造の骨格となる成分であり、含有量は一方のガラス粉末総量１００質量％に対し、２０質量％以上、４５質量％以下であるのが好ましい。含有量が２０質量％より少ないと、化学的な安定性が低下し、特性がばらついてしまう場合がある。また、４５質量％より多いと軟化点が上がり過ぎてしまう場合がある。 [Component Composition of Si-B-Al-Ba-Zn-O-Based Glass Powder of the Present Invention]
The composition of one glass powder of the present invention will be described in detail.
<SiO 2 >
SiO 2 is a component that serves as a skeleton of one glass powder structure of the present invention, and the content thereof is preferably 20% by mass or more and 45% by mass or less with respect to 100% by mass of one glass powder. When the content is less than 20% by mass, chemical stability may be lowered and characteristics may vary. On the other hand, if it exceeds 45% by mass, the softening point may increase too much.
＜Ｂ2Ｏ3＞
　Ｂ2Ｏ3も本発明の一方のガラス粉末構造の骨格となる成分で、ガラスの軟化点を下げる効果がある。
　その含有量は一方のガラス粉末総量１００質量％に対し、５質量％以上、１２質量％以下である。含有量が５質量％より少ないと、ガラスの靱性が低下してクラックを生じ易くなる。一方、１２質量％より多く含有しすぎると分相を起こし易く、ガラスが水に溶けやすくなる。また、抵抗体の抵抗温度係数が負の値になりやすくなってしまい、±１００ｐｐｍ／℃以内の０付近に調整するのが困難になってしまう。 <B 2 O 3 >
B 2 O 3 is also a component that becomes a skeleton of one glass powder structure of the present invention, and has an effect of lowering the softening point of glass.
The content is 5% by mass or more and 12% by mass or less with respect to 100% by mass of one glass powder. If the content is less than 5% by mass, the toughness of the glass is lowered and cracks are likely to occur. On the other hand, when it contains more than 12 mass%, it will be easy to raise | generate a phase separation and glass will melt | dissolve in water easily. In addition, the resistance temperature coefficient of the resistor tends to be a negative value, and it becomes difficult to adjust the resistance to around 0 within ± 100 ppm / ° C.
＜Ａｌ2Ｏ3＞
　Ａｌ2Ｏ3は本発明の一方のガラス粉末の耐久性を向上させる働きを有するもので、その含有量は一方のガラス粉末総量１００質量％に対し、５質量％以上、２０質量％以下であるのが好ましい。含有量が５質量％より少ないと、ガラスの分相が起こりやすく、ガラスの耐久性が低下してしまう場合がある。２０質量％より多いと、軟化点が上がり過ぎてしまう場合がある。 <Al 2 O 3 >
Al 2 O 3 has a function of improving the durability of one glass powder of the present invention, and its content is 5% by mass or more and 20% by mass or less with respect to 100% by mass of one glass powder. Is preferred. When the content is less than 5% by mass, phase separation of the glass tends to occur, and the durability of the glass may be lowered. If it is more than 20% by mass, the softening point may increase too much.
＜ＢａＯ＞
　ＢａＯは本発明の鉛を含有しない一方のガラスで軟化点を下げる働きがあり、かつ、誘電率を高くし、電圧をかけた際の絶縁性を高める効果がある。
　その含有量は一方のガラス粉末総量１００質量％に対し、４質量％以上、３５質量％以下であるのが好ましい。含有量が４質量％より少ないと、ガラスの軟化点を十分に下げる事ができない場合がある。３５質量％より多いと、ガラスの耐久性が低下してしまう場合がある。 <BaO>
BaO has the function of lowering the softening point in one glass of the present invention that does not contain lead, and has the effect of increasing the dielectric constant and enhancing the insulation when a voltage is applied.
The content thereof is preferably 4% by mass or more and 35% by mass or less with respect to 100% by mass of one glass powder. If the content is less than 4% by mass, the softening point of the glass may not be lowered sufficiently. When it is more than 35% by mass, the durability of the glass may be lowered.
＜ＺｎＯ＞
　ＺｎＯも本発明の鉛を含有しない一方のガラスで軟化点を下げる働きがある。その含有量は一方のガラス粉末総量１００質量％に対し、５質量％以上、３５質量％以下であるのが好ましい。含有量が５質量％より少ないと、ガラスの軟化点を十分に下げる事ができない場合がある。３５質量％より多いと、ガラスの耐久性が低下してしまう場合がある。 <ZnO>
ZnO also has a function of lowering the softening point in one glass containing no lead of the present invention. The content is preferably 5% by mass or more and 35% by mass or less with respect to 100% by mass of one glass powder. If the content is less than 5% by mass, the softening point of the glass may not be lowered sufficiently. When it is more than 35% by mass, the durability of the glass may be lowered.
＜その他のガラス粉末成分＞
　Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系ガラス粉末の必須成分は、ＳｉＯ2、Ｂ2Ｏ3、Ａｌ2Ｏ3、ＢａＯ、ＺｎＯであるが、その他の成分を含有させても良く、例として以下のようなものが挙げられる。
　ＣａＯはＢａＯと同様に軟化点を下げる成分として使用する事ができる。
　Ｂｉ2Ｏ3を用いる事によってもガラスの軟化点を下げる事ができるが、多く含有させると結晶化しやすくなり、各種特性が悪化する場合があるため添加量に注意が必要である。
　また、ガラスの化学的な安定性を高める目的でＺｒＯ2を含有させても良いが、多量に含有させるとガラスの軟化点を下げる事ができなくなり、軟化点が高くなり過ぎてしまう場合がある。
　Ｋ、Ｎａ、Ｌｉのアルカリ金属酸化物も軟化点を下げる目的ではその効果が大きいが、ガラスの絶縁性が低下して抵抗体の負荷特性が低下するため、添加する際は抵抗体の電気的特性の低下が問題ない範囲での添加が望ましい。 <Other glass powder components>
The essential components of the Si—B—Al—Ba—Zn—O-based glass powder are SiO 2 , B 2 O 3 , Al 2 O 3 , BaO, and ZnO, but other components may be included. The following may be mentioned.
CaO can be used as a component that lowers the softening point, like BaO.
By using Bi 2 O 3 , the softening point of the glass can be lowered. However, if it is contained in a large amount, it becomes easy to crystallize, and various characteristics may be deteriorated, so the addition amount needs attention.
Further, ZrO 2 may be contained for the purpose of enhancing the chemical stability of the glass, but if it is contained in a large amount, the softening point of the glass cannot be lowered and the softening point may become too high. .
Alkali metal oxides of K, Na and Li are also effective for the purpose of lowering the softening point. However, since the insulating properties of the glass are lowered and the load characteristics of the resistor are lowered, the electrical properties of the resistor are added when added. Addition within a range where there is no problem in deterioration of characteristics is desirable.
［本発明のＳｉ－Ｂ－Ａｌ－Ｂａ－Ｏ系ガラス粉末の成分組成］
　続いて、本発明の他方のガラス粉末の組成について詳細に説明する。
＜ＳｉＯ2＞
　ＳｉＯ2は本発明の他方のガラス構造の骨格となる成分であり、その含有量は他方のガラス粉末総量１００質量％に対し、２０質量％以上、３８質量％以下であるのが好ましい。含有量が２０質量％より少ないと、化学的な安定性が低下し、３８質量％より多いと、軟化点が上がり過ぎてしまう場合がある。 [Component Composition of Si-B-Al-Ba-O Glass Powder of the Present Invention]
Subsequently, the composition of the other glass powder of the present invention will be described in detail.
<SiO 2 >
SiO 2 is a component that becomes the skeleton of the other glass structure of the present invention, and the content thereof is preferably 20% by mass or more and 38% by mass or less with respect to 100% by mass of the other glass powder. When the content is less than 20% by mass, the chemical stability is lowered. When the content is more than 38% by mass, the softening point may be excessively increased.
＜Ｂ2Ｏ3＞
　Ｂ2Ｏ3も本発明の他方のガラス構造の骨格となる成分であり、ガラスの軟化点を下げる効果を有している。その含有量は他方のガラス粉末総量１００質量％に対し、１４質量％以上、２５質量％以下である。含有量が１４質量％より少ないと、抵抗体の抵抗温度係数が負の値になりやすくなる。一方、２５質量％より多く含有すると、ガラスが水に溶けやすくなる。 <B 2 O 3 >
B 2 O 3 is also a component that becomes the skeleton of the other glass structure of the present invention, and has an effect of lowering the softening point of the glass. The content is 14% by mass or more and 25% by mass or less with respect to 100% by mass of the other glass powder. When the content is less than 14% by mass, the resistance temperature coefficient of the resistor tends to be a negative value. On the other hand, when it contains more than 25 mass%, glass will melt | dissolve in water easily.
＜Ａｌ2Ｏ3＞
　Ａｌ2Ｏ3は本発明の他方のガラスの耐久性を向上させる働きを示すもので、その含有量は他方のガラス粉末総量１００質量％に対し、５質量％以上、１５質量％以下であるのが好ましい。含有量が５質量％より少ないと、ガラスの分相が起こりやすくなり、ガラスの耐久性の低下を招いてしまう場合がある。一方、１５質量％より多いと、軟化点が上がり過ぎてしまう場合がある。 <Al 2 O 3 >
Al 2 O 3 functions to improve the durability of the other glass of the present invention, and its content is 5% by mass or more and 15% by mass or less with respect to 100% by mass of the other glass powder. Is preferred. When the content is less than 5% by mass, phase separation of the glass tends to occur, and the durability of the glass may be lowered. On the other hand, if the amount is more than 15% by mass, the softening point may increase too much.
＜ＢａＯ＞
　ＢａＯは本発明の鉛を含有しない他方のガラスでは軟化点を下げる働きがあり、誘電率が高く電圧をかけた際の絶縁性を高める効果がある。その含有量は他方のガラス粉末総量１００質量％に対し、４質量％以上３５質量％以下であるのが好ましい。含有量が４質量％より少ないと、ガラスの軟化点が高くなり、３５質量％より多いと、ガラスの耐久性が低下してしまう場合がある。 <BaO>
BaO has a function of lowering the softening point in the other glass of the present invention that does not contain lead, and has an effect of increasing the insulation when a voltage is applied because of its high dielectric constant. The content is preferably 4% by mass or more and 35% by mass or less with respect to 100% by mass of the other glass powder. When the content is less than 4% by mass, the softening point of the glass is increased, and when it is more than 35% by mass, the durability of the glass may be lowered.
＜その他のガラス粉末＞
　Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｏ系ガラス粉末の必須成分は、ＳｉＯ2、Ｂ2Ｏ3、Ａｌ2Ｏ3、ＢａＯであるが、その他の成分を含有させても良く、例として以下の様なものが挙げられる。
　ＺｎＯは、ＢａＯと同様に軟化点を下げるために使用する事ができる。このＺｎＯは先に説明した一方の「Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系ガラス粉末」では必須成分であるが、もう一方の他方のガラス粉末ではＢ2Ｏ3の含有率が高く、十分に軟化点を下げる事ができるため必須成分ではない。
　ＣａＯは、ＢａＯと同様に軟化点を下げる成分として使用する事ができる。
　鉛の代わりにＢｉ2Ｏ3を用いる事によってガラスの軟化点を下げる事ができるが、多く含有させると結晶化しやすくなり、各種特性が悪化する場合があるため添加量に注意が必要である。
　また、ガラスの化学的な安定性を高める目的でＺｒＯ2を含有させても良いが、多量に含有させるとガラスの軟化点を下げる事ができなくなり、軟化点が高くなり過ぎてしまう場合がある。 <Other glass powder>
The essential components of the Si—B—Al—Ba—O glass powder are SiO 2 , B 2 O 3 , Al 2 O 3 and BaO, but other components may be included. The thing is mentioned.
ZnO can be used for lowering the softening point, like BaO. This ZnO is an essential component in one “Si—B—Al—Ba—Zn—O-based glass powder” described above, but the other glass powder has a high B 2 O 3 content, Since the softening point can be lowered sufficiently, it is not an essential component.
CaO can be used as a component that lowers the softening point in the same manner as BaO.
By using Bi 2 O 3 instead of lead, the softening point of the glass can be lowered. However, if it is contained in a large amount, it becomes easy to crystallize, and various characteristics may be deteriorated.
Further, ZrO 2 may be contained for the purpose of enhancing the chemical stability of the glass, but if it is contained in a large amount, the softening point of the glass cannot be lowered and the softening point may become too high. .
　Ｋ、Ｎａ、Ｌｉのアルカリ金属酸化物も軟化点を下げる目的ではその効果が大きいが、ガラスの絶縁性が低下して抵抗体の負荷特性が低下するため、添加する際は抵抗体の電気的特性の低下が問題ない範囲での添加が望ましい。 Alkali metal oxides of K, Na and Li are also effective for the purpose of lowering the softening point. However, since the insulating properties of the glass are lowered and the load characteristics of the resistor are lowered, the electrical properties of the resistor are added when added. Addition within a range where there is no problem in deterioration of characteristics is desirable.
　「Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系ガラス粉末」と「Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｏ系ガラス粉末」の割合は、目的とする抵抗値と抵抗温度係数から任意に選択する事ができるが、抵抗温度係数が負の値になりやすい抵抗値の高い領域では「Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系ガラス粉末」の割合を多くし、抵抗温度係数が正の値になりやすい抵抗値の低い領域では「Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｏ系ガラス粉末」の割合を多くする。 The ratio of “Si—B—Al—Ba—Zn—O-based glass powder” and “Si—B—Al—Ba—O-based glass powder” can be arbitrarily selected from the target resistance value and resistance temperature coefficient. However, the ratio of “Si—B—Al—Ba—Zn—O-based glass powder” is increased in the region where the temperature coefficient of resistance tends to be negative, and the resistance temperature coefficient is set to a positive value. In the region where the resistance value tends to be low, the ratio of “Si—B—Al—Ba—O-based glass powder” is increased.
　以上、ガラス粉末の成分組成について説明してきたが、その形態について、以下詳細に説明する。
＜ガラス粉末の粒径＞
　ガラス粉末の粒径は特に規定されず、使用目的に応じて選定すれば良いが、大きすぎると抵抗体の抵抗値ばらつきが増大したり、負荷特性が低下したりする原因となるので好ましくない。これらを避けるために、ガラス粉末の平均粒径を３μｍ以下とする事が好ましく、１．５μｍ以下とする事がより好ましい。
　３μｍより大きいガラス粉末は、粉砕する事により小粒径化する事ができるが、この粒径を得るためのガラスの粉砕には、ボールミル、遊星ミル、ビーズミルなど用いる事ができる。粉砕したガラス粉末の粒度をシャープにするには湿式粉砕を用いる事が好ましい。 As mentioned above, although the component composition of glass powder has been demonstrated, the form is demonstrated in detail below.
<Grain size of glass powder>
The particle size of the glass powder is not particularly defined and may be selected according to the purpose of use. However, if the particle size is too large, the resistance value variation of the resistor increases or the load characteristics deteriorate, which is not preferable. In order to avoid these, the average particle size of the glass powder is preferably 3 μm or less, and more preferably 1.5 μm or less.
Glass powders larger than 3 μm can be reduced in size by pulverization. For pulverization of the glass to obtain this particle size, a ball mill, a planetary mill, a bead mill, or the like can be used. In order to sharpen the particle size of the pulverized glass powder, it is preferable to use wet pulverization.
　次に、上記ガラス粉末以外の抵抗体用組成物の構成成分について説明する。
＜導電粒子＞
　本発明で使用する導電粒子の、鉛を含有しないルテニウム系導電粒子としては、酸化ルテニウムを用いるのが好ましい。一般に、鉛を含有しないガラス粉末と、導電粒子として酸化ルテニウムを用いて形成した抵抗体の抵抗温度係数は負の値になりやすく、抵抗値も低くなり過ぎる課題があるが、本発明の抵抗体用組成物の構成とする事で、その課題を解決する事ができた。
　その導電粒子として用いる酸化ルテニウムは、比表面積が５ｍ2／ｇ以上１５０ｍ2／ｇ以下のものを用いる事が好ましい。一般に比表面積が大きい導電粒子を用いると抵抗体の出現抵抗値が低く、同抵抗値で比較すると抵抗温度係数も低くなる傾向があるので、目的とする抵抗値に応じて適切な粒径を選択するのが好ましい。 Next, the constituent components of the resistor composition other than the glass powder will be described.
<Conductive particles>
Of the conductive particles used in the present invention, ruthenium-based conductive particles containing no lead are preferably ruthenium oxide. In general, the resistance temperature coefficient of a glass powder not containing lead and a resistor formed using ruthenium oxide as a conductive particle tends to be a negative value, and the resistance value is too low. By adopting the composition of the composition for use, the problem could be solved.
The ruthenium oxide used as the conductive particles preferably has a specific surface area of 5 m 2 / g or more and 150 m 2 / g or less. In general, when conductive particles with a large specific surface area are used, the resistance value of the resistor is low, and the resistance temperature coefficient tends to be low when compared with the same resistance value. Select the appropriate particle size according to the target resistance value. It is preferable to do this.
　導電粒子としては、酸化ルテニウム以外には、ルテニウム酸ビスマス、ルテニウム酸カルシウム、ルテニウム酸ストロンチウム、ルテニウム酸バリウムなどを用いる事ができる。必要に応じて２種類以上の上記導電粒子の混合物や、ルテニウム系以外の導電粒子を上記導電粒子に混合して用いる事もできる。 As the conductive particles, besides ruthenium oxide, bismuth ruthenate, calcium ruthenate, strontium ruthenate, barium ruthenate and the like can be used. If necessary, a mixture of two or more kinds of the above conductive particles or a conductive particle other than ruthenium can be mixed with the above conductive particles.
＜導電粒子とガラス粉末の比率＞
　所望する抵抗値等によって、ルテニウム系導電粒子とガラス粉末の比率は変える事ができる。通常は、ルテニウム系導電粒子の質量：２種類のガラス粉末の合計質量＝５０：５０～５：９５の範囲である。
　導電粒子がこれより多いと厚膜抵抗体の膜構造が脆くなり、温度サイクルなどで抵抗値が変化しやすくなったり、経時変化を起こしやすくなったりする場合があるので好ましくない。また、導電粒子がこれより少ないと抵抗温度係数が負の値になりやすくなり、０に近づけるのが困難となる場合があるので好ましくない。 <Ratio of conductive particles to glass powder>
The ratio between the ruthenium-based conductive particles and the glass powder can be changed depending on the desired resistance value and the like. Usually, the mass of the ruthenium-based conductive particles: the total mass of the two types of glass powders = 50: 50 to 5:95.
If there are more conductive particles than this, the film structure of the thick film resistor becomes fragile, and the resistance value is likely to change due to a temperature cycle or the like, and the change with time is likely to occur. On the other hand, if the number of conductive particles is less than this, the temperature coefficient of resistance tends to be a negative value, and it may be difficult to approach 0, which is not preferable.
＜添加剤＞
　本発明の抵抗体用組成物には、抵抗体の抵抗値や抵抗温度係数や負荷特性、トリミング性の改善、調整を目的として一般に使用される添加剤を加えても良い。
　代表的な添加剤としては、Ｎｂ2Ｏ5、Ｔａ2Ｏ5、ＴｉＯ2、ＣｕＯ、ＭｎＯ2、ＺｒＯ2、Ａｌ2Ｏ3、ＳｉＯ2、ＺｒＳｉＯ4等が挙げられる。これらの添加剤を加える事でより優れた特性を有する抵抗体を作製する事ができる。
　その添加剤の含有量は目的によって調整されるが、導電粒子とガラス粉末の合計１００質量部に対して通常１０質量部以下である。 <Additives>
To the resistor composition of the present invention, an additive generally used for the purpose of improving or adjusting the resistance value, resistance temperature coefficient, load characteristic, trimming property of the resistor may be added.
Typical additives include Nb 2 O 5 , Ta 2 O 5 , TiO 2 , CuO, MnO 2 , ZrO 2 , Al 2 O 3 , SiO 2 , ZrSiO 4 and the like. By adding these additives, a resistor having more excellent characteristics can be produced.
Although the content of the additive is adjusted depending on the purpose, it is usually 10 parts by mass or less with respect to 100 parts by mass in total of the conductive particles and the glass powder.
＜有機ビヒクル＞
　導電粒子とガラス粉末は、必要に応じて添加剤を加えた上で、印刷用の抵抗体ペーストとするために有機ビヒクル中に混合、分散される。
　使用する有機ビヒクルには特に制限はなく、通常ターピネオール、ブチルカルビトール、ブチルカルビトールアセテート等の溶剤にエチルセルロース、アクリル酸エステル、メタアクリル酸エステル、ロジン、マレイン酸エステル等の樹脂を溶解した溶液が用いられる。また、必要に応じて、分散剤や可塑剤などを加える事ができる。 <Organic vehicle>
The conductive particles and the glass powder are mixed and dispersed in an organic vehicle in order to obtain a resistor paste for printing after adding additives as necessary.
The organic vehicle to be used is not particularly limited, and a solution in which a resin such as ethyl cellulose, acrylic acid ester, methacrylic acid ester, rosin, maleic acid ester is dissolved in a solvent such as terpineol, butyl carbitol, or butyl carbitol acetate is usually used. Used. Moreover, a dispersing agent, a plasticizer, etc. can be added as needed.
　導電粒子、ガラス粉末、添加剤等を有機ビヒクルに分散する方法は特に制限されず、微細な粒子を分散させるのに一般的に用いられている３本ロールミルやビーズミル、遊星ミル等を用いる事ができる。
　有機ビヒクルの含有量は、印刷や塗布方法によって適宣調整されるが、導電粒子、ガラス粉末、添加剤の合計１００質量部に対して２０～２００質量部程度である。 The method for dispersing the conductive particles, glass powder, additives and the like in the organic vehicle is not particularly limited, and a three-roll mill, a bead mill, a planetary mill or the like generally used for dispersing fine particles may be used. it can.
The content of the organic vehicle is appropriately adjusted depending on the printing and coating method, but is about 20 to 200 parts by mass with respect to 100 parts by mass in total of the conductive particles, glass powder, and additives.
　本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。
［試験１：ガラス粉末の特性評価］
　まず、各種組成のガラス粉末を作製し、各ガラス粉末の軟化点、及び平均粒径を測定した。
　結晶化が激しいガラス粉末を抵抗体に用いると、抵抗体の抵抗値のばらつきが大きく、電気的特性も低下するため、本発明の抵抗体用組成物として使用する事は出来ないため、本評価で用いたガラス粉末は、事前に結晶化がほとんど確認されなかったガラス組成を用いている。 The present invention will be specifically described, but the present invention is not limited to these examples.
[Test 1: Characteristic evaluation of glass powder]
First, glass powders having various compositions were prepared, and the softening point and average particle diameter of each glass powder were measured.
When glass powder that is heavily crystallized is used for the resistor, the resistance value variation of the resistor is large and the electrical characteristics are also deteriorated. Therefore, it cannot be used as the resistor composition of the present invention. The glass powder used in the above has a glass composition in which almost no crystallization was confirmed in advance.
　軟化点が８００℃を超すなどの、軟化点が高すぎるガラスを抵抗体に用いると、抵抗体の抵抗値のばらつきが大きく、電気的特性も低下するため、本発明の抵抗体用組成物として使用する事は出来ない。そのため、各ガラス粉末の軟化点を測定した。
　軟化点の測定は、ＴＧ－ＤＴＡ（セイコー電子社製ＴＧ／ＤＴＡ３２０型）を用い、ＤＴＡ曲線を測定し、得られたＤＴＡ曲線の第三変曲点から求められる値を軟化点とした。
　また、ガラス粉末の平均粒径には、レーザー回折式粒度分布測定によるＤ５０の値を用いた。
　本評価に供したガラス粉末の組成、軟化点、平均粒径を表１に示す。 When a glass having a too high softening point, such as a softening point exceeding 800 ° C., is used for the resistor, the resistance value varies greatly and the electrical characteristics also deteriorate. It cannot be used. Therefore, the softening point of each glass powder was measured.
The softening point was measured using TG-DTA (TG / DTA320 type manufactured by Seiko Denshi Co., Ltd.), the DTA curve was measured, and the value obtained from the third inflection point of the obtained DTA curve was taken as the softening point.
Moreover, the value of D50 by the laser diffraction type particle size distribution measurement was used for the average particle diameter of glass powder.
Table 1 shows the composition, softening point, and average particle size of the glass powder subjected to this evaluation.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
［試験２：抵抗体用組成物評価］
　実施例と比較例では、２種類の比表面積の酸化ルテニウム粒子からなる導電粒子とガラス粉末の合計１００質量部に対し、４３質量部の有機ビヒクルを加えて、３本ロールミルで十分に分散させて抵抗体ペーストを作製した。酸化ルテニウム粒子とガラス粉末の比率は抵抗体の面積抵抗値がおよそ０．１ｋΩ／□、１ｋΩ／□、１０ｋΩ／□、１００ｋΩ／□となるように調整した。
　即ち、実施例１では比表面積１５ｍ2／ｇのＲｕＯ2粉とＡ－１及びＢ－１を混合したガラス粉末を使用し、実施例２では比表面積９０ｍ2／ｇのＲｕＯ2粉とＡ－２及びＢ－２を混合したガラス粉末を使用した。また、比較例１では比表面積１５ｍ2／ｇのＲｕＯ2粉とＡ－１ガラス粉末を使用し、比較例２では比表面積１５ｍ2／ｇのＲｕＯ2粉とＢ－１ガラス粉末を使用し、比較例３では比表面積９０ｍ2／ｇのＲｕＯ2粉とＡ－２ガラス粉末を使用し、比較例４では比表面積９０ｍ2／ｇのＲｕＯ2粉とＢ－２ガラス粉末を使用した。 [Test 2: Evaluation of resistor composition]
In Examples and Comparative Examples, 43 parts by mass of an organic vehicle is added to a total of 100 parts by mass of conductive particles composed of ruthenium oxide particles having two specific surface areas and glass powder, and the mixture is sufficiently dispersed by a three roll mill. A resistor paste was prepared. The ratio of the ruthenium oxide particles to the glass powder was adjusted so that the resistance values of the resistors were approximately 0.1 kΩ / □, 1 kΩ / □, 10 kΩ / □, and 100 kΩ / □.
That is, in Example 1, glass powder obtained by mixing RuO 2 powder having a specific surface area of 15 m 2 / g and A-1 and B-1 was used, and in Example 2, RuO 2 powder having a specific surface area of 90 m 2 / g and A— Glass powder mixed with 2 and B-2 was used. Further, by using the RuO 2 powder and A-1 Glass powder of Comparative Example 1, a specific surface area of 15 m 2 / g, using the RuO 2 powder and B-1 glass powder in Comparative Example 2 a specific surface area of 15 m 2 / g, using the RuO 2 powder and a-2 glass powder in Comparative example 3 a specific surface area of 90m 2 / g, it was used RuO 2 powder and B-2 glass powder in Comparative example 4 a specific surface area of 90m 2 / g.
　次に、予めアルミナ基板に焼成して形成した１質量％Ｐｄ、９９質量％Ａｇの組成からなる５対の電極間に、作製した抵抗体ペーストを印刷し、１５０℃×５分で乾燥した後、ピーク温度８５０℃×９分、トータル３０分で焼成し厚膜抵抗体を形成した。厚膜抵抗体のサイズは抵抗体幅が１．０ｍｍ、抵抗体長さ（電極間）を１．０ｍｍとなるようにした。この様な基板を各試料同じ条件で５枚作製した。 Next, after printing the prepared resistor paste between five pairs of electrodes having a composition of 1% by mass Pd and 99% by mass Ag previously formed by firing on an alumina substrate and drying at 150 ° C. for 5 minutes A thick film resistor was formed by firing at a peak temperature of 850 ° C. × 9 minutes for a total of 30 minutes. The thick film resistor had a resistor width of 1.0 mm and a resistor length (between electrodes) of 1.0 mm. Five such substrates were prepared under the same conditions for each sample.
　形成された厚膜抵抗体に関して、それぞれ膜厚、及び抵抗値を測定し、膜厚を７μｍとした場合の換算面積抵抗値、２５℃から－５５℃までの抵抗温度係数（Ｃｏｌｄ－ＴＣＲ：以下、Ｃ－ＴＣＲ）、２５℃から１２５℃までの抵抗温度係数（ＨＯＴ－ＴＣＲ：以下、Ｈ－ＴＣＲ）を算出した。 With respect to the formed thick film resistor, the film thickness and the resistance value are measured, respectively, the converted area resistance value when the film thickness is 7 μm, the temperature coefficient of resistance from 25 ° C. to −55 ° C. (Cold-TCR: below) C-TCR), a temperature coefficient of resistance (HOT-TCR: hereinafter referred to as H-TCR) from 25 ° C. to 125 ° C. was calculated.
　膜厚は、任意のアルミナ基板を１枚抽出し、触針式の厚み粗さ計でアルミナ基板上に形成されている５個の厚膜抵抗体の膜厚を測定し、その平均した値をその試料全体の「実測膜厚」とした。 The film thickness is obtained by extracting one arbitrary alumina substrate, measuring the thickness of five thick film resistors formed on the alumina substrate with a stylus type thickness roughness meter, and calculating the average value. The “measured film thickness” of the entire sample was used.
　面積抵抗値は、５枚のアルミナ基板上に形成した５個の厚膜抵抗体、合計２５個の厚膜抵抗体の抵抗値を測定した値の平均値と上記「実測膜厚」から算出した値を、膜厚を７μｍとした場合の「換算面積抵抗値」で算出し直して評価した。
　その算出は、２５個の厚膜抵抗体の抵抗値を四端子法にて測定した実測値の平均値を「実測抵抗値」とした場合、以下の式（１）を用いて算出した。なお、本評価において「換算膜厚」は「７μｍ」を用いた。 The area resistance value was calculated from the average value of the measured resistance values of five thick film resistors formed on five alumina substrates, a total of 25 thick film resistors, and the above “measured film thickness”. The value was recalculated and evaluated by the “converted area resistance value” when the film thickness was 7 μm.
The calculation was performed using the following formula (1), where the average value of the measured values obtained by measuring the resistance values of the 25 thick film resistors by the four-terminal method was “measured resistance value”. In this evaluation, “7 μm” was used as the “equivalent film thickness”.
Figure JPOXMLDOC01-appb-M000002
Figure JPOXMLDOC01-appb-M000002
　抵抗温度係数は、厚膜抵抗体を－５５℃、２５℃、１２５℃にそれぞれ１５分保持してから抵抗値を測定し、それぞれの抵抗値をＲ-55、Ｒ25、Ｒ125とした時に下記の式（２）、（３）に示す計算式によって算出した値で、それぞれ５個の厚膜抵抗体から算出した値の平均値を用いた。 The temperature coefficient of resistance is determined when the resistance value is measured after holding the thick film resistor at −55 ° C., 25 ° C., and 125 ° C. for 15 minutes, and the respective resistance values are R −55 , R 25 , and R 125. The average values of the values calculated from the five thick film resistors were used, which were values calculated by the following formulas (2) and (3).
Figure JPOXMLDOC01-appb-M000003
Figure JPOXMLDOC01-appb-M000003
　上記算出方法により得られた各試料の、換算膜厚抵抗値、抵抗温度係数（Ｃ－ＴＣＲ、Ｈ－ＴＣＲ）の値を、各試料に用いたＲｕＯ2の比表面積、及び抵抗体ペースト作製時の抵抗体用組成物の含有量と共に表２に示す。 For each sample obtained by the above calculation method, the converted film thickness resistance value and the resistance temperature coefficient (C-TCR, H-TCR) value, the specific surface area of RuO 2 used for each sample, and the resistor paste preparation Table 2 shows the content of the resistor composition.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表１及び表２からもわかるように、実施例１と比較例１及び２には、比表面積１５ｍ2／ｇの酸化ルテニウム粒子を用い、実施例１ではＳｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系ガラス粉末「Ａ－１」と、Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｏ系ガラス粉末「Ｂ－１」の両方のガラス粉末を用い、比較例１及び２ではどちらか１種類のガラス粉末のみを用いている。 As can be seen from Tables 1 and 2, in Example 1 and Comparative Examples 1 and 2, ruthenium oxide particles having a specific surface area of 15 m 2 / g were used. In Example 1, Si—B—Al—Ba—Zn— Both the O-type glass powder “A-1” and the Si—B—Al—Ba—O-type glass powder “B-1” were used. In Comparative Examples 1 and 2, only one type of glass powder was used. Is used.
　比較例１では、面積抵抗値が１．１ｋΩ／□以下の「抵抗値が低い領域」で抵抗温度係数が５８１ｐｐｍ／℃以上と正の値に大きくなり過ぎて、調整剤を用いても±１００ｐｐｍ／℃にする事が難しい事がわかる。比較例２では、面積抵抗値が０．９５ｋΩ／□以上の「抵抗値が比較的高い領域」で抵抗温度係数が－１７５ｐｐｍ／℃以下の負の値になってしまい、±１００ｐｐｍ／℃にする事ができない。 In Comparative Example 1, the resistance temperature coefficient is too large to be 581 ppm / ° C. or more in an “area where the resistance value is low” where the sheet resistance value is 1.1 kΩ / □ or less, and even if a regulator is used, ± 100 ppm. It turns out that it is difficult to set to / ℃. In Comparative Example 2, the resistance temperature coefficient becomes a negative value of −175 ppm / ° C. or less in the “region where the resistance value is relatively high” having an area resistance value of 0.95 kΩ / □ or more, and is ± 100 ppm / ° C. I can't do anything.
　これらに対して、実施例１では０．０８７ｋΩ／□から１１０ｋΩ／□の面積抵抗値領域で抵抗温度係数が５２～２０１ｐｐｍ／℃の範囲であり、酸化マンガン、酸化ニオブ、酸化チタンなどの調整剤を添加する事によって容易に±１００ｐｐｍ／℃に調整する事が可能である事がわかる。 On the other hand, in Example 1, the temperature coefficient of resistance is in the range of 52 to 201 ppm / ° C. in the area resistance value region of 0.087 kΩ / □ to 110 kΩ / □, and a regulator such as manganese oxide, niobium oxide, titanium oxide, or the like. It can be seen that it can be easily adjusted to ± 100 ppm / ° C. by adding.
　また、実施例２と比較例３及び４には、比表面積９０ｍ2／ｇの酸化ルテニウム粒子を用い、実施例２ではＳｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系のガラス粉末「Ａ－２」と、Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｏ系のガラス粉末「Ｂ－２」の両方のガラス粉末を用い、比較例３及び４ではどちらか１種類のガラス粉末のみを用いている。 In Example 2 and Comparative Examples 3 and 4, ruthenium oxide particles having a specific surface area of 90 m 2 / g were used. In Example 2, the Si—B—Al—Ba—Zn—O-based glass powder “A-2” was used. And Si—B—Al—Ba—O glass powder “B-2”, and in Comparative Examples 3 and 4, only one type of glass powder is used.
　比較例３でも、面積抵抗値が１ｋΩ／□以下の「抵抗値が低い領域」で抵抗温度係数が５９９ｐｐｍ／℃以上と正の値に大きくなり過ぎて、調整剤を用いても±１００ｐｐｍ／℃にする事が困難である事がわかる。また比較例４では、面積抵抗値が１ｋΩ／□以上の「抵抗値が比較的高い領域」で抵抗温度係数が－２５０ｐｐｍ／℃以下の負の値になってしまい、±１００ｐｐｍ／℃にする事ができない。 Even in Comparative Example 3, the resistance temperature coefficient is too high at 599 ppm / ° C. or more in the “resistance low region” where the sheet resistance value is 1 kΩ / □ or less, and even if a regulator is used, ± 100 ppm / ° C. It turns out that it is difficult to do. Further, in Comparative Example 4, the resistance temperature coefficient becomes a negative value of −250 ppm / ° C. or less in the “region where the resistance value is relatively high” having an area resistance value of 1 kΩ / □ or more, and is set to ± 100 ppm / ° C. I can't.
　これに対して、実施例２では、０．０８５ｋΩ／□から１１０ｋΩ／□の面積抵抗値領域で抵抗温度係数が２１～１４５ｐｐｍ／℃の範囲であり、酸化マンガン、酸化ニオブ、酸化チタンなどの調整剤を添加する事によって容易に±１００ｐｐｍ／℃に調整する事ができる事がわかる。 On the other hand, in Example 2, the temperature coefficient of resistance is in the range of 21 to 145 ppm / ° C. in the area resistance value region of 0.085 kΩ / □ to 110 kΩ / □, and adjustment of manganese oxide, niobium oxide, titanium oxide, etc. It can be seen that it can be easily adjusted to ± 100 ppm / ° C. by adding an agent.
　表１、表２に示す実施例、比較例からわかるように、本発明によれば、従来困難であったルテニウム系導電粒子とガラス粉末を原料とする厚膜抵抗体の抵抗温度係数を、低い抵抗値領域から高い抵抗値領域に渡って、±１００ｐｐｍ／℃以内に容易に調整する事が可能である事がわかる。 As can be seen from the Examples and Comparative Examples shown in Tables 1 and 2, according to the present invention, the temperature coefficient of resistance of the thick film resistor using ruthenium-based conductive particles and glass powder as raw materials, which has been difficult in the past, is low. It can be seen that the adjustment can be easily made within ± 100 ppm / ° C. from the resistance value region to the high resistance value region.

Claims (6)

  1. 　鉛を含有しないルテニウム系導電粒子と、
    　　少なくとも２種類の、鉛を含有しないガラス粉末を含む抵抗体用組成物であって、
    　　　ガラス粉末の一種が、ＳｉＯ2、Ｂ2Ｏ3、Ａｌ2Ｏ3、ＢａＯ、ＺｎＯを含むＳｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系ガラス粉末で、前記Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系ガラス粉末の総量１００質量％に対し、Ｂ2Ｏ3を５質量％以上、１２質量％以下含有し、
    　　　ガラス粉末の他の一種が、ＳｉＯ2、Ｂ2Ｏ3、Ａｌ2Ｏ3、ＢａＯを含むＳｉ－Ｂ－Ａｌ－Ｂａ－Ｏ系ガラス粉末で、前記Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｏ系ガラス粉末の総量１００質量％に対し、Ｂ2Ｏ3を１４質量％以上、２５質量％以下含有する事を特徴とする抵抗体用組成物。     Ruthenium-based conductive particles containing no lead,
    A resistor composition comprising at least two types of lead-free glass powder,
    One type of glass powder is Si—B—Al—Ba—Zn—O glass powder containing SiO 2 , B 2 O 3 , Al 2 O 3 , BaO, ZnO, and the Si—B—Al—Ba—Zn glass powder. the total amount 100 mass% of -O-based glass powder, B 2 O 3 of 5 wt% or more, containing 12 wt% or less,
    Another kind of glass powder is Si—B—Al—Ba—O glass powder containing SiO 2 , B 2 O 3 , Al 2 O 3 , BaO, and the Si—B—Al—Ba—O glass. A resistor composition comprising B 2 O 3 in an amount of 14% by mass to 25% by mass with respect to 100% by mass of the total amount of powder.
  2. 　前記Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系ガラス粉末の成分組成が、Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｚｎ－Ｏ系ガラス粉末の総量１００質量％に対し、ＳｉＯ2を２０質量％以上、４５質量％以下、Ｂ2Ｏ3を５質量％以上、１２質量％以下、Ａｌ2Ｏ3を５質量％以上、２０質量％以下、ＢａＯを４質量％以上、３５質量％以下、ＺｎＯを５質量％以上、３５質量％以下含有し、
    　　前記Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｏ系ガラス粉末の成分組成が、Ｓｉ－Ｂ－Ａｌ－Ｂａ－Ｏ系ガラス粉末の総量１００質量％に対し、ＳｉＯ2を２０質量％以上、３８質量％以下、Ｂ2Ｏ3を１４質量％以上、２５質量％以下、Ａｌ2Ｏ3を５質量％以上、１５質量％以下、ＢａＯを４質量％以上、３５質量％以下含有する事を特徴とする請求項１に記載の抵抗体用組成物。     The component composition of the Si—B—Al—Ba—Zn—O-based glass powder is 20% by mass or more of SiO 2 with respect to 100% by mass of the total amount of Si—B—Al—Ba—Zn—O-based glass powder. 45 wt% or less, B 2 O 3 of 5 wt% or more, 12 wt% or less, Al 2 O 3 of 5 wt% or more, 20 wt% or less, BaO 4 mass% or more, 35 wt% or less, 5 ZnO Containing not less than 35% by mass and not more than 35% by mass,
    The component composition of the Si—B—Al—Ba—O glass powder is 20 mass% or more and 38 mass% or less of SiO 2 with respect to 100 mass% of the total amount of the Si—B—Al—Ba—O glass powder. , B 2 O 3 of 14 wt% or more, 25 wt% or less, Al 2 O 3 of 5 wt% or more, 15 wt% or less, BaO 4 mass% or more, claims, characterized in that contains more than 35 wt% Item 2. The resistor composition according to Item 1.
  3. 　前記鉛を含有しないルテニウム系導電粒子が、酸化ルテニウム（ＲｕＯ2）である事を特徴とする請求項１又は２に記載の抵抗体用組成物。 3. The resistor composition according to claim 1, wherein the lead-free ruthenium-based conductive particles are ruthenium oxide (RuO 2 ).
  4. 　前記酸化ルテニウム（ＲｕＯ2）の比表面積が、５ｍ2／ｇ以上、１５０ｍ2／ｇ以下である事を特徴とする請求項３に記載の抵抗体用組成物。 4. The resistor composition according to claim 3, wherein the ruthenium oxide (RuO 2 ) has a specific surface area of 5 m 2 / g or more and 150 m 2 / g or less.
  5. 　請求項１～４のいずれか１項に記載の抵抗体用組成物と有機ビヒクルを含み、前記抵抗体用組成物が、有機ビヒクル中に分散して含有している事を特徴とする抵抗体ペースト。 5. A resistor comprising the resistor composition according to claim 1 and an organic vehicle, wherein the resistor composition is dispersed in the organic vehicle. paste.
  6. 　セラミック基板上に形成された、請求項５に記載の抵抗体ペーストの焼成体である事を特徴とする厚膜抵抗体。 A thick film resistor, which is a fired body of the resistor paste according to claim 5 formed on a ceramic substrate.
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