WO2018088333A1 - Glass dielectric - Google Patents

Glass dielectric Download PDF

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Publication number
WO2018088333A1
WO2018088333A1 PCT/JP2017/039784 JP2017039784W WO2018088333A1 WO 2018088333 A1 WO2018088333 A1 WO 2018088333A1 JP 2017039784 W JP2017039784 W JP 2017039784W WO 2018088333 A1 WO2018088333 A1 WO 2018088333A1
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WIPO (PCT)
Prior art keywords
component
glass
less
dielectric
present
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PCT/JP2017/039784
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French (fr)
Japanese (ja)
Inventor
杰 傅
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株式会社オハラ
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Publication of WO2018088333A1 publication Critical patent/WO2018088333A1/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • 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
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • 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
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
    • 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
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/16—Compositions for glass with special properties for dielectric glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics

Definitions

  • the present invention relates to a glass that has a high dielectric constant and dielectric breakdown strength, and is suitably used as a dielectric material for circuit boards and electronic components, large-capacity high-voltage capacitors, and the like that are mounted on communication devices and electronic devices.
  • Patent Document 1 discloses that SiO 2 is 40 to 65 mol%, MgO, CaO, SrO and BaO are at least one 20 to 45 mol%, and at least one of TiO 2 and ZrO 2 is 5 -25 mol%, NbO 5/2 0.5 to 15 mol%, the total amount of these oxides is 85 mol% or more, and the dielectric constant (1 MHz, 25 ° C.) is 9 or more.
  • a glass composition having is described.
  • the dielectric constant at 1 to 5 GHz is 18 or more, the content of TeO 2 is 50 to 95 mol%, and Na 2 O, BaO, ZnO, MoO 3 , Al 2 O 3 , a high dielectric constant tellurite glass containing 5 to 50 mol% of one or more selected from Nb 2 O 5 , Sb 2 O 3 and Bi 2 O 3 is described.
  • the dielectric breakdown strength tends to decrease as the dielectric constant increases. That is, the dielectric constant and the dielectric breakdown strength are in a trade-off relationship, and it is difficult to increase both.
  • the present inventor has intensively studied and found a glass dielectric that can solve the above-mentioned problems with a composition system different from the existing technology, and has completed the present invention.
  • the present invention includes the following (1) to (6). (1) 15.0% to 40.0% of P 2 O 5 component in mol% with respect to the total amount of substances in oxide equivalent composition TiO 2 component 1.0% to 40.0%, Nb 2 O 5 component 5.0% to 40.0%, Molar sum (BaO + ZnO) 3.0% to 50.0% And a dielectric constant at 1 kHz of 20 or more.
  • a glass dielectric having a high dielectric constant and a high dielectric breakdown strength can be provided.
  • the P 2 O 5 component is 15.0% to 40.0% in terms of mol% with respect to the total amount of substances having an oxide equivalent composition
  • TiO 2 component 1.0% to 40.0% TiO 2 component 1.0% to 40.0%
  • Nb 2 O 5 component 5.0% to 40.0% Molar sum (BaO + ZnO) 3.0% to 50.0%
  • a dielectric constant ⁇ at 1 kHz is 20 or more.
  • glass dielectric of the present invention such glass is also referred to as “glass dielectric of the present invention”.
  • the glass dielectric of the present invention has a high dielectric constant and a high dielectric breakdown strength, it is suitably used as a dielectric material for circuit boards, electronic parts, large-capacity high-voltage capacitors, and the like.
  • the glass dielectric of the present invention can be used as a dielectric for high-temperature capacitors because the characteristics at high temperatures (generally 90 ° C. or higher) are unlikely to deteriorate.
  • the composition range of each component constituting the glass dielectric of the present invention is described below. In the following, when “%” is simply described, it means “mol%”.
  • the glass composition represented by “%” in the specification of the present application means the percentage of the total amount of substances in the oxide conversion composition.
  • the “oxide equivalent composition” refers to a composition that assumes that oxides, nitrates, and the like used as raw materials for the glass dielectric constituent of the present invention are all decomposed and changed into oxides by melting. Therefore, the “percentage of the total substance amount of the oxide equivalent composition” means that the total mass of the generated oxide when all the components are present as oxides is 100 mol%, and the abundance of each component relative to it Means.
  • outer percent means not included in the “total amount of oxide-converted composition”, and the ratio of the outer percent refers to the total mass of the above-mentioned generated oxides of 100 mol%. It is assumed that the abundance with respect to this is expressed as a percentage.
  • the P 2 O 5 component is an indispensable component for the glass dielectric of the present invention because it constitutes a glass network structure and improves the stability of the glass.
  • glass can be more stably produced by containing 15.0% or more of the P 2 O 5 component. If it is less than 15.0%, it becomes difficult to produce glass. Therefore, the content of the P 2 O 5 component is preferably 15.0% or more, more preferably 18.0% or more, and further preferably 20.0% or more.
  • the content of the P 2 O 5 component is preferably 40.0% or less, more preferably 38.0% or less, and even more preferably 35.0% or less.
  • the TiO 2 component has the effect of increasing the stability and dielectric constant of the glass and is an essential component in the glass dielectric of the present invention. If the content of this component is too high, the stability of the glass tends to decrease. Therefore, the content is preferably 40.0% or less, more preferably 35.0% or less, and more preferably 30.0%. More preferably, it is contained below. On the other hand, in order to obtain the above effect, the lower limit addition amount is preferably 1.0% or more, more preferably 3.0% or more, and 5.0% or more. Further preferred.
  • the Nb 2 O 5 component has the effect of increasing the stability and dielectric constant of the glass, and is an essential component in the glass dielectric of the present invention.
  • a desired dielectric constant can be obtained by containing 5.0% or more of the Nb 2 O 5 component. Therefore, the content of the Nb 2 O 5 component is preferably 5.0% or more, more preferably 7.0% or more, and still more preferably 10.0% or more.
  • the content of the Nb 2 O 5 component is 40.0% or less, glass can be stably produced. Therefore, the content of the P 2 O 5 component is preferably 40.0% or less, more preferably 38.0% or less, and even more preferably 35.0% or less.
  • the molar sum (TiO 2 + Nb 2 O 5 ), that is, the total of the content (%) of TiO 2 and the content (%) of Nb 2 O 5 is 25.0% or more. Preferably, it is 30.0% or more, more preferably 35.0% or more. Further, the total is preferably 70.0% or less, more preferably 60.0% or less, and further preferably 58.0% or less. If this total amount is too high, the stability of the glass tends to decrease, and conversely, if it is too low, the dielectric constant tends to decrease.
  • the total amount of BaO component and ZnO component (BaO + ZnO) 50.0% or less the stability and dielectric properties of the glass are hardly deteriorated, so the total amount of BaO component and ZnO component is preferably 50.0%. More preferably, the upper limit is 40.0%, and most preferably 37.0%.
  • the total amount is preferably 3.0%, more preferably 5.0. %, More preferably 7.0%, and most preferably 9.0%.
  • the molar sum of Nb 2 O 5 component, TiO 2 component and BaO component is preferably 35.0% or more, and 38.0% or more. It is more preferable that it is 40.0% or more. When this total amount (mol sum) is too low, the dielectric constant tends to be low.
  • the total amount (mole sum) is preferably 80.0% or less, more preferably 68.0% or less, and further preferably 65.0% or less. When this total amount (mole sum) is too high, the stability of the glass tends to decrease.
  • the SiO 2 component has an effect of increasing the stability of the glass and is an optional component in the glass dielectric of the present invention.
  • the specific content is preferably 20.0% or less, more preferably 10.0% or less, and even more preferably 5.0% or less. If this component content is too high, the stability of the glass tends to decrease.
  • the B 2 O 3 component has an effect of increasing the stability of the glass and is an optional component in the glass dielectric of the present invention.
  • the specific content is preferably 20.0% or less, more preferably 10.0% or less, more preferably 7.0% or less, and 5.0% or less. Further preferred. If this component content is too high, the stability of the glass tends to decrease.
  • the Al 2 O 3 component has an effect of increasing the stability of the glass and is an optional component in the glass dielectric of the present invention.
  • the specific content is preferably 10.0% or less, more preferably 8.0% or less, and even more preferably 5.0% or less. If this component content is too high, the stability of the glass tends to decrease.
  • the ZnO component has an effect of increasing the meltability, stability and dielectric constant of glass, and is a component that can be arbitrarily added to the glass dielectric of the present invention. Therefore, it may be contained preferably in an amount exceeding 0%, more preferably 1.0% or more, and further preferably 3.0% or more. On the other hand, if the content of this component is too high, the stability of the glass tends to decrease. Therefore, the content is preferably 30.0% or less, more preferably 28.0% or less, 25 More preferably, the content is 0.0% or less.
  • the BaO component has an effect of increasing the meltability, stability, and dielectric constant of glass, and is a component that can be arbitrarily added to the glass dielectric of the present invention. Therefore, it may be contained more preferably than 0%, more preferably 5.0% or more, and still more preferably 10.0% or more. On the other hand, if this component is too high, the stability of the glass tends to decrease, so it is preferably 30.0% or less, more preferably 28.0% or less, and even more preferably 25.0% or less.
  • the SrO component has an effect of increasing the meltability, stability, and dielectric constant of glass, and is a component that can be arbitrarily added to the glass dielectric of the present invention. If the content of this component is too high, the stability of the glass tends to decrease. Therefore, the content is preferably 30.0% or less, more preferably 25.0% or less, and more preferably 20.0%. More preferably, it is contained below.
  • the CaO component has an effect of enhancing the meltability and stability of the glass, and can be optionally added to the glass dielectric of the present invention. If the content of this component is too high, the stability of the glass tends to decrease. Therefore, the content is preferably 30.0% or less, more preferably 25.0% or less, and more preferably 20.0%. More preferably, it is contained below.
  • the MgO component has an effect of improving the meltability and stability of the glass, and can be optionally added to the glass dielectric of the present invention. If the content of this component is too high, the stability of the glass tends to decrease. Therefore, the content is preferably 30.0% or less, more preferably 20.0% or less, and more preferably 15.0%. More preferably, it is contained below.
  • the glass dielectric of the present invention is an RO component (in the formula, R is one or more selected from the group consisting of Mg, Ca, Sr, and Ba) with respect to the total amount of the oxide-converted composition. Is preferably 50.0% or less, more preferably 40.0% or less, and even more preferably 37.0% or less. When the content of the RO component is in the above range, the stability and dielectric properties of the glass tend to be improved.
  • R is one or more selected from the group consisting of Mg, Ca, Sr, and Ba
  • the Li 2 O component has an effect of increasing the stability of the glass and is an optional component in the glass dielectric of the present invention.
  • the specific content is preferably 10.0% or less, more preferably 5.0% or less, and further preferably 3.0% or less. If this component content is too high, the dielectric breakdown strength of the glass tends to decrease.
  • the Na 2 O component has an effect of increasing the stability of the glass and is an optional component in the glass dielectric of the present invention.
  • the specific content is preferably 10.0% or less, more preferably 5.0% or less, and further preferably 3.0% or less. If this component content is too high, the dielectric breakdown strength of the glass tends to decrease.
  • the K 2 O component has an effect of increasing the stability of the glass and is an optional component in the glass dielectric of the present invention.
  • the specific content is preferably 15.0% or less, more preferably 8.0% or less, and even more preferably 5.0% or less. If this component content is too high, the dielectric constant and dielectric breakdown strength of the glass tend to decrease.
  • the glass dielectric of the present invention is 10.0% because the total amount of the Rn 2 O component (wherein Rn is one or more selected from the group consisting of Li, Na and K) does not decrease the dielectric breakdown strength. Or less, more preferably 5.0% or less, still more preferably 3.0% or less, and most preferably not contained.
  • the molar ratio (ZnO + MgO + Rn 2 O) / (TiO 2 + Nb 2 O 5 ) is preferably 0.7 or less, more preferably 0.65 or less, and 0.63 or less. More preferably. If this component content is too high, the dielectric properties are likely to deteriorate.
  • the WO 3 component is effective in improving the stability and dielectric constant of glass, and is an optional component in the glass dielectric of the present invention.
  • the specific content is preferably 20% or less, more preferably 10.0% or less, and even more preferably 8.0% or less. If this component content is too high, the stability of the glass tends to decrease.
  • the Ta 2 O 5 component is effective in improving the stability and dielectric constant of glass, and is an optional component in the glass dielectric of the present invention.
  • the specific content is preferably 15.0% or less, more preferably 10.0% or less, more preferably 5.0% or less, and 3.0% or less. Further preferred. If this component content is too high, the stability of the glass tends to decrease.
  • the ZrO 2 component is an optional component in the glass dielectric of the present invention because it is effective in improving the stability and dielectric constant of the glass.
  • the specific content is preferably 15.0% or less, more preferably 10.0% or less, more preferably 8.0% or less, and 5.0% or less. Further preferred. If this component content is too high, the stability of the glass tends to decrease.
  • the SnO 2 component is an optional component in the glass dielectric of the present invention because it is effective in improving the dielectric properties.
  • the specific content is preferably 10.0% or less, more preferably 5.0% or less, and further preferably 3.0% or less. If this component content is too high, the stability of the glass tends to decrease.
  • the Ln 2 O 3 component (wherein Ln is at least one selected from the group consisting of La, Ce, Gd, Y, Dy, Yb, and Lu) is effective in improving dielectric properties, and the glass of the present invention It is an optional component in the dielectric.
  • the total of these contents (mole sum) is preferably 10.0% or less, more preferably 5.0% or less, and even more preferably 3.0% or less. If the content of these components is too high, the stability of the glass tends to decrease.
  • the M x O y component (one or more selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo) is effective in improving the dielectric properties, and the glass dielectric of the present invention.
  • the total of these contents (molar sum) is preferably 10.0% or less, more preferably 5.0% or less, more preferably 3.0% or less, and 1.0% More preferably, it is as follows. If the content of these components is too high, the stability of the glass tends to decrease.
  • the F component is an optional component in the glass dielectric of the present invention because it increases the stability of the glass.
  • the content is preferably 30.0% or less, more preferably 15.0% or less, and even more preferably 8.0% or less. If the content of this component is too high, the dielectric properties and the dielectric breakdown strength tend to be reduced.
  • the Sb 2 O 3 component is an optional component in the glass dielectric of the present invention because it has the effect of a glass defoamer and contributes to the improvement of the dielectric properties.
  • the specific content is preferably 10.0% or less, more preferably 5.0% or less, more preferably 3.0% or less, and 1.0% or less. Further preferred. If this component content is too high, the stability of the glass tends to decrease.
  • the glass dielectric of the present invention has a dielectric constant ⁇ of 20 or more at 1 kHz.
  • the dielectric constant ⁇ is preferably 21 or more, and more preferably 24 or more.
  • the dielectric constant and dielectric loss were measured over a frequency range of 10 Hz to 1 MHz using an impedance analyzer (for example, SI1260 manufactured by Solartron), and the value at 1 kHz was defined as the dielectric constant and dielectric loss of the present invention.
  • the glass dielectric of the present invention can be formed into an arbitrary shape, it can be used as various dielectrics.
  • it is used for dielectric materials such as circuit boards and electronic components, large-capacity high-voltage capacitors mounted on communication devices and electronic devices.
  • the capacitor is used for current fluctuation buffering, coupling and smoothing in the power converter.
  • High-voltage capacitors are indispensable components for excimer laser equipment used in semiconductor processing and vision correction surgery, medical X-ray equipment, industrial high-voltage power supplies, and renewable energy transmission systems.
  • These glasses can be used in the form of being combined with other dielectrics in the form of fibers, powders, pastes, etc., in addition to being used alone for the above-mentioned purposes.
  • a dielectric substrate having a patterned electrode formed on the substrate, a laminated substrate material, a dielectric resonator element, a firing aid for the dielectric material, a dielectric paste (dielectric powder in a vehicle made of an organic compound, etc.
  • the suspension is generally used after being formed on an electrode by screen printing or punching printing).
  • the glass dielectric of this invention will not be specifically limited if it is a method of manufacturing normal glass, For example, it can manufacture by the following method.
  • a predetermined amount of each starting material (oxide, carbonate, nitrate, phosphate, sulfate, etc.) is weighed and mixed uniformly.
  • the mixed raw materials are put into a quartz crucible, an alumina crucible or a platinum crucible and melted in a melting furnace at a temperature range of 1200 to 1450 ° C. for 1 to 12 hours. Then, after stirring and homogenizing, it is lowered to an appropriate temperature and cast into a mold or the like to produce glass.
  • the glass sheet When used as a fiber, the glass sheet is remelted to obtain glass fibers, but the glass fibers may be obtained directly from the initial solution.
  • the molded bulk glass when used as a ceramic dielectric firing aid, filler or dielectric paste, the molded bulk glass may be crushed, or cullet is obtained by pouring water from the first solution into water. May be.
  • Example 1 Composition: 25P 2 O 5 -15TiO 2 -25Nb 2 O 5 -15BaO-3SrO-10CaO-7ZnO (mol%)
  • the raw materials (TiO 2 , Nb 2 O 5 , Ba (PO 3 ) 2 , Sr (NO 3 ) 2 , Ca (PO 3 ) 2 , ZnO) were prepared and mixed well so as to have the above composition, and then quartz It put into the crucible and melt
  • the obtained glass was processed to about 30 mm ⁇ 30 mm ⁇ 1 mm, gold electrodes were vapor-deposited on both sides, and dielectric characteristics were evaluated by an impedance analyzer (SI1260 manufactured by Solartron). The result is shown in FIG. From this figure, it can be seen that the dielectric constant and dielectric loss of the glass of this composition hardly changed with frequency.
  • the dielectric constant ⁇ and dielectric loss at 1 kHz were 27 and 0.0040, respectively.
  • the dielectric breakdown strength was 79 kV / mm.
  • the dielectric breakdown strength was measured according to JIS C 2141 using a sample having a thickness of 1 mm.
  • Examples 2 to 25 and Comparative Example 1 were produced in the same manner as in Example 1.
  • the compositions and dielectric properties of the examples and comparative examples are summarized in Tables 1 to 4.
  • the dielectric breakdown strength is summarized in Table 5. It can be seen that the glass dielectric of the present invention has the same dielectric constant as in Example 1, but the dielectric loss is an order of magnitude lower and the dielectric breakdown strength is more than doubled.

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Abstract

The problem is to provide a glass ceramic having a high dielectric constant as well as high dielectric breakdown strength. This problem is solved by a glass dielectric characterized by containing, in mol%, 15.0%-40.0% of a P2O5 component, 1.0%-40.0% of a TiO2 component, 5.0%-40.0% of an Nb2O5 component, and a molar sum (BaO + ZnO) of 3.0%-50.0% relative to the total mass of the composition in terms of oxides and having a dielectric constant at 1 kHz of 20 or higher.

Description

ガラス誘電体Glass dielectric
　本発明は、誘電率と絶縁破壊強度とがいずれも高く、通信機器や電子機器に搭載される回路基板及び電子部品、大容量高電圧コンデンサーなどの誘電材料として好適に用いられるガラスに関する。 The present invention relates to a glass that has a high dielectric constant and dielectric breakdown strength, and is suitably used as a dielectric material for circuit boards and electronic components, large-capacity high-voltage capacitors, and the like that are mounted on communication devices and electronic devices.
　近年、自動車用電話やパーソナル無線に代表される移動体通信、携帯電話、衛星放送、衛星通信、ＣＡＴＶ等に代表されるような高度情報化時代を迎え、情報伝達はより高速化・高周波化の傾向にあり、さらにこれらの機器には小型化が求められ、これに伴って回路素子に対しても小型化が強く要求されている。 In recent years, with the advent of advanced information typified by mobile communications such as automobile telephones and personal radio, mobile phones, satellite broadcasting, satellite communications, CATV, etc., information transmission has become faster and higher in frequency. In addition, these devices are required to be downsized, and accordingly, downsizing of circuit elements is also strongly demanded.
　例えば、マイクロ波用回路素子について、その大きさは、使用電磁波の波長が基準になる。すなわち、誘電率（ε）の誘電体中を伝播する電磁波の波長（λ）は、真空中の波長をλ0とするとλ＝λ0／（ε1/2）となり、λはεの平方根に反比例する。よってマイクロ波用回路素子の小型化のためには、誘電率が高い材料が求められている。 For example, for a microwave circuit element, the size is based on the wavelength of the electromagnetic wave used. That is, the wavelength (λ) of an electromagnetic wave propagating through a dielectric having a dielectric constant (ε) is λ = λ 0 / (ε 1/2 ) where λ 0 is the wavelength in vacuum, and λ is the square root of ε. Inversely proportional. Therefore, a material having a high dielectric constant is required for miniaturization of microwave circuit elements.
　また、半導体加工や視力矯正手術で利用されるエキシマレーザー、医療用Ｘ線、蓄電装置（工業用高電圧電源、電気自動車の起動電源など）、送電設備などに使われる高エネルギー貯蔵密度を有するコンデンサーへの需要が近年に高まっている。コンデンサーのエネルギー貯蔵密度が（１／２）×ε0εrＥ2（ε0：真空の誘電率、εr：材料の誘電率、Ｅ：絶縁破壊強度）で表されるので、高いエネルギー貯蔵密度を得ようとするには高い誘電率と高い絶縁破壊強度を併せ持つ誘電体が望まれる。 In addition, excimer lasers used in semiconductor processing and vision correction surgery, medical X-rays, power storage devices (industrial high-voltage power supplies, start-up power supplies for electric vehicles, etc.), capacitors with high energy storage density used in power transmission facilities, etc. The demand for is increasing in recent years. Since the energy storage density of the capacitor is expressed by (1/2) × ε 0 ε r E 2 (ε 0 : dielectric constant of vacuum, ε r : dielectric constant of material, E: dielectric breakdown strength), high energy storage In order to obtain the density, a dielectric having both a high dielectric constant and a high dielectric breakdown strength is desired.
　誘電率が高いガラスとして、例えば特許文献１には、ＳｉＯ2を４０～６５モル％、ＭｇＯ，ＣａＯ，ＳｒＯおよびＢａＯの少なくともひとつを２０～４５モル％、ＴｉＯ2およびＺｒＯ2の少なくともひとつを５～２５モル％、ＮｂＯ5/2を０．５～１５モル％それぞれ含み、これらの酸化物の合計量が８５モル％以上であり、比誘電率（１ＭＨｚ，２５℃）９以上の繊維化適性を有するガラス組成物が記載されている。
　また、例えば特許文献２には、１～５ＧＨｚでの誘電率が１８以上であり、ＴｅＯ2の含有量は５０～９５ｍｏｌ％であり、さらにＮａ2Ｏ、ＢａＯ、ＺｎＯ、ＭｏＯ3、Ａｌ2Ｏ3、Ｎｂ2Ｏ5、Ｓｂ2Ｏ3、Ｂｉ2Ｏ3から選択された１種以上を５～５０ｍｏｌ％含有する高誘電率テルライトガラスが記載されている。 As a glass having a high dielectric constant, for example, Patent Document 1 discloses that SiO 2 is 40 to 65 mol%, MgO, CaO, SrO and BaO are at least one 20 to 45 mol%, and at least one of TiO 2 and ZrO 2 is 5 -25 mol%, NbO 5/2 0.5 to 15 mol%, the total amount of these oxides is 85 mol% or more, and the dielectric constant (1 MHz, 25 ° C.) is 9 or more. A glass composition having is described.
Further, for example, in Patent Document 2, the dielectric constant at 1 to 5 GHz is 18 or more, the content of TeO 2 is 50 to 95 mol%, and Na 2 O, BaO, ZnO, MoO 3 , Al 2 O 3 , a high dielectric constant tellurite glass containing 5 to 50 mol% of one or more selected from Nb 2 O 5 , Sb 2 O 3 and Bi 2 O 3 is described.
特開平５－６３３２３号公報Japanese Patent Laid-Open No. 5-63323 特開２００５－２８１０２３号公報JP 2005-281023 A
　しかしながら、従来、誘電率が大きい材料ほど絶縁破壊強度は低下する傾向が知られている。すなわち、誘電率と絶縁破壊強度はトレードオフの関係にあり、いずれをも高めることは困難であった。 However, conventionally, it is known that the dielectric breakdown strength tends to decrease as the dielectric constant increases. That is, the dielectric constant and the dielectric breakdown strength are in a trade-off relationship, and it is difficult to increase both.
　本発明者は鋭意検討し、既存の技術と異なった組成系で上記の課題を解決することができるガラス誘電体を見出し、本発明を完成させた。
　本発明は以下の（１）～（６）である。
（１）酸化物換算組成の全物質量に対して、モル％で
　Ｐ2Ｏ5成分　１５．０％～４０．０％、
　ＴｉＯ2成分　１．０％～４０．０％、
　Ｎｂ2Ｏ5成分　５．０％～４０．０％、
　モル和（ＢａＯ＋ＺｎＯ）　３．０％～５０．０％
を含有し、１ｋＨｚにおける誘電率が２０以上であることを特徴とするガラス誘電体。
（２）酸化物換算組成の全物質量に対して、モル％で
　ＳｉＯ2成分　０～２０．０％、
　Ｂ2Ｏ3成分　０～２０．０％、
　Ａｌ2Ｏ3成分　０～１０．０％、
　ＺｎＯ成分　０～３０．０％、
　ＢａＯ成分　０～３０．０％、
　ＳｒＯ成分　０～３０．０％、
　ＣａＯ成分　０～３０．０％、
　ＭｇＯ成分　０～３０．０％、
　Ｌｉ2Ｏ成分　０～１０．０％、
　Ｎａ2Ｏ成分　０～１０．０％、
　Ｋ2Ｏ成分　０～１５．０％、
　ＷＯ3成分　０～２０．０％、
　Ｔａ2Ｏ5成分　０～１５．０％
　ＺｒＯ2成分　０～１５．０％
　ＳｎＯ２成分　０～１０．０％、
　Ｓｂ2Ｏ3成分　０～１０．０％、
　外割でＦを０～３０．０％
を含有することを特徴とする上記（１）に記載のガラス誘電体。
（３）酸化物換算組成の全物質量に対して、モル％で
　Ｌｎ2Ｏ3成分（式中、ＬｎはＬａ、Ｃｅ、Ｇｄ、Ｙ、Ｄｙ、Ｙｂ、Ｌｕからなる群より選択される１種以上）のモル和が１０．０％以下であり、
　ＲＯ成分（式中、ＲはＭｇ、Ｃａ、Ｓｒ、Ｂａからなる群より選択される１種以上）のモル和が５０．０％以下であり、
　Ｒｎ2Ｏ成分（式中、ＲｎはＬｉ、Ｎａ、Ｋからなる群より選択される１種以上）のモル和が１０．０％以下であり、
　ＭxＯy成分（Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ａｇ、Ｍｏからなる群より選択される１種以上）のモル和が１０．０％以下である、上記（１）または（２）に記載のガラス誘電体。
（４）酸化物換算組成のＮｂ2Ｏ5成分、ＴｉＯ2成分およびＢａＯ成分のモル和（Ｎｂ2Ｏ5成分＋ＴｉＯ2成分＋ＢａＯ成分）が３５．０～８０．０％である、上記（１）から（３）のいずれかに記載のガラス誘電体。
（５）モル比（ＺｎＯ＋ＭｇＯ＋Ｒｎ2Ｏ）／（ＴｉＯ2＋Ｎｂ2Ｏ5）が０．７以下である、上記（１）から（４）のいずれかに記載のガラス誘電体。
（６）モル和（ＴｉＯ2＋Ｎｂ2Ｏ5）が２５．０～７０．０％である、上記（１）から（５）のいずれかに記載のガラス誘電体。 The present inventor has intensively studied and found a glass dielectric that can solve the above-mentioned problems with a composition system different from the existing technology, and has completed the present invention.
The present invention includes the following (1) to (6).
(1) 15.0% to 40.0% of P 2 O 5 component in mol% with respect to the total amount of substances in oxide equivalent composition
TiO 2 component 1.0% to 40.0%,
Nb 2 O 5 component 5.0% to 40.0%,
Molar sum (BaO + ZnO) 3.0% to 50.0%
And a dielectric constant at 1 kHz of 20 or more.
(2) 0 to 20.0% of SiO 2 component in mol% with respect to the total amount of substances of oxide conversion composition,
B 2 O 3 component 0-20.0%,
Al 2 O 3 component 0 to 10.0%,
ZnO component 0-30.0%,
BaO component 0-30.0%,
SrO component 0-30.0%,
CaO component 0-30.0%,
MgO component 0-30.0%,
Li 2 O component 0 to 10.0%,
Na 2 O component 0 to 10.0%,
K 2 O component 0 to 15.0%,
WO 3 component 0-20.0%,
Ta 2 O 5 component 0 ～ 15.0%
ZrO 2 component 0 ～ 15.0%
SnO 2 component 0-10.0%,
Sb 2 O 3 component 0 to 10.0%,
0% to 30.0% for F
The glass dielectric according to (1) above, which contains
(3) Ln 2 O 3 component in mol% with respect to the total amount of substances in oxide equivalent composition (wherein Ln is selected from the group consisting of La, Ce, Gd, Y, Dy, Yb, Lu) The molar sum of the species or more) is 10.0% or less,
The molar sum of the RO component (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, Ba) is 50.0% or less,
The molar sum of the Rn 2 O component (wherein Rn is one or more selected from the group consisting of Li, Na and K) is 10.0% or less,
The above (1), wherein the molar sum of the M x O y component (one or more selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo) is 10.0% or less. Or the glass dielectric as described in (2).
(4) The above (1), wherein the molar sum (Nb 2 O 5 component + TiO 2 component + BaO component) of the Nb 2 O 5 component, TiO 2 component and BaO component of the oxide conversion composition is 35.0 to 80.0% ) To (3).
(5) The glass dielectric according to any one of (1) to (4), wherein the molar ratio (ZnO + MgO + Rn 2 O) / (TiO 2 + Nb 2 O 5 ) is 0.7 or less.
(6) The glass dielectric according to any one of (1) to (5), wherein the molar sum (TiO 2 + Nb 2 O 5 ) is 25.0 to 70.0%.
　本発明によれば、誘電率が高く、かつ、絶縁破壊強度も高いガラス誘電体を提供することができる。 According to the present invention, a glass dielectric having a high dielectric constant and a high dielectric breakdown strength can be provided.
実施例の誘電特性の測定結果を示す図である。It is a figure which shows the measurement result of the dielectric property of an Example.
　本発明について説明する。
　本発明は、酸化物換算組成の全物質量に対して、モル％で
　Ｐ2Ｏ5成分　１５．０％～４０．０％、
　ＴｉＯ2成分　１．０％～４０．０％、
　Ｎｂ2Ｏ5成分　５．０％～４０．０％、
　モル和（ＢａＯ＋ＺｎＯ）　３．０％～５０．０％
を含有し、１ｋＨｚにおける誘電率εが２０以上であることを特徴とするガラス誘電体である。
　このようなガラスを以下では「本発明のガラス誘電体」ともいう。 The present invention will be described.
In the present invention, the P 2 O 5 component is 15.0% to 40.0% in terms of mol% with respect to the total amount of substances having an oxide equivalent composition,
TiO 2 component 1.0% to 40.0%,
Nb 2 O 5 component 5.0% to 40.0%,
Molar sum (BaO + ZnO) 3.0% to 50.0%
And a dielectric constant ε at 1 kHz is 20 or more.
Hereinafter, such glass is also referred to as “glass dielectric of the present invention”.
　本発明のガラス誘電体は誘電率が高く、かつ、絶縁破壊強度も高いため、回路基板及び電子部品、大容量高電圧コンデンサーなどの誘電材料として好適に用いられる。また、本発明のガラス誘電体は、高温（おおむね９０℃以上）の特性が劣化しにくので、高温用コンデンサーの誘電体としても利用できる。 Since the glass dielectric of the present invention has a high dielectric constant and a high dielectric breakdown strength, it is suitably used as a dielectric material for circuit boards, electronic parts, large-capacity high-voltage capacitors, and the like. In addition, the glass dielectric of the present invention can be used as a dielectric for high-temperature capacitors because the characteristics at high temperatures (generally 90 ° C. or higher) are unlikely to deteriorate.
＜ガラス成分＞
　本発明のガラス誘電体を構成する各成分の組成範囲を以下に述べる。
　以下において単に「％」と記した場合、「モル％」を意味するものとする。
　また、本願明細書中において「％」で表されるガラス組成は、すべて酸化物換算組成の全物質量における百分率を意味するものとする。ここで、「酸化物換算組成」とは、本発明のガラス誘電体構成成分の原料として使用される酸化物、硝酸塩等が、溶融によってすべて分解され酸化物へ変化すると仮定した組成をいう。したがって「酸化物換算組成の全物質量における百分率」は、すべての成分が酸化物として存在しているとしたときの生成酸化物の質量の総和を１００モル％とし、それに対する各成分の存在量を意味する。
　なお、以下において「外割」とは、上記の「酸化物換算組成の全物質量」に含めないことを意味し、外割の比率は、上記の生成酸化物の質量の総和を１００モル％としたときの、これに対する存在量を百分率で表した値を意味するものとする。 <Glass component>
The composition range of each component constituting the glass dielectric of the present invention is described below.
In the following, when “%” is simply described, it means “mol%”.
In addition, the glass composition represented by “%” in the specification of the present application means the percentage of the total amount of substances in the oxide conversion composition. Here, the “oxide equivalent composition” refers to a composition that assumes that oxides, nitrates, and the like used as raw materials for the glass dielectric constituent of the present invention are all decomposed and changed into oxides by melting. Therefore, the “percentage of the total substance amount of the oxide equivalent composition” means that the total mass of the generated oxide when all the components are present as oxides is 100 mol%, and the abundance of each component relative to it Means.
In the following description, “outer percent” means not included in the “total amount of oxide-converted composition”, and the ratio of the outer percent refers to the total mass of the above-mentioned generated oxides of 100 mol%. It is assumed that the abundance with respect to this is expressed as a percentage.
　Ｐ2Ｏ5成分は、ガラスの網目構造を構成し、ガラスの安定性を高めるので本発明のガラス誘電体に欠かせない成分である。特に、Ｐ2Ｏ5成分を１５．０％以上含有することで、より安定的にガラスを作製することができる。１５．０％未満であるとガラスの作製が困難となる。従って、Ｐ2Ｏ5成分の含有量は、好ましくは１５．０％以上、より好ましくは１８．０％以上、さらに好ましくは２０．０％以上とする。
　他方で、Ｐ2Ｏ5成分の含有量を４０．０％以下にすることで、所望の誘電率をより容易に得ることができる。従って、Ｐ2Ｏ5成分の含有量は、好ましくは４０．０%以下、より好ましくは３８．０％以下、さらに好ましくは３５．０％以下とする。 The P 2 O 5 component is an indispensable component for the glass dielectric of the present invention because it constitutes a glass network structure and improves the stability of the glass. In particular, glass can be more stably produced by containing 15.0% or more of the P 2 O 5 component. If it is less than 15.0%, it becomes difficult to produce glass. Therefore, the content of the P 2 O 5 component is preferably 15.0% or more, more preferably 18.0% or more, and further preferably 20.0% or more.
On the other hand, by setting the content of the P 2 O 5 component to 40.0% or less, a desired dielectric constant can be obtained more easily. Therefore, the content of the P 2 O 5 component is preferably 40.0% or less, more preferably 38.0% or less, and even more preferably 35.0% or less.
　ＴｉＯ2成分はガラスの安定性と誘電率を高める効果があり、本発明のガラス誘電体における必須成分である。この成分の含有率が高すぎるとガラスの安定性が低下しやすくなる傾向があるので、４０．０％以下含有することが好ましく、３５．０％以下含有することがより好ましく、３０．０％以下含有することがさらに好ましい。一方、上述の効果を得ようとするには、下限の添加量は１．０％以上であることが好ましく、３．０％以上であることがより好ましく、５．０％以上であることがさらに好ましい。 The TiO 2 component has the effect of increasing the stability and dielectric constant of the glass and is an essential component in the glass dielectric of the present invention. If the content of this component is too high, the stability of the glass tends to decrease. Therefore, the content is preferably 40.0% or less, more preferably 35.0% or less, and more preferably 30.0%. More preferably, it is contained below. On the other hand, in order to obtain the above effect, the lower limit addition amount is preferably 1.0% or more, more preferably 3.0% or more, and 5.0% or more. Further preferred.
　Ｎｂ2Ｏ5成分はガラスの安定性と誘電率を高める効果があり、本発明のガラス誘電体における必須成分である。特に、Ｎｂ2Ｏ5成分を５．０％以上含有することで、所望の誘電率を得ることができる。従って、Ｎｂ2Ｏ5成分の含有量は、好ましくは５．０％以上、より好ましくは７．０％以上、さらに好ましくは１０．０％以上とする。
　他方で、Ｎｂ2Ｏ5成分の含有量を４０．０％以下にすることで、安定的にガラスを作製することができる。従って、Ｐ2Ｏ5成分の含有量は、好ましくは４０．０%以下、より好ましくは３８．０％以下、さらに好ましくは３５．０％以下とする。 The Nb 2 O 5 component has the effect of increasing the stability and dielectric constant of the glass, and is an essential component in the glass dielectric of the present invention. In particular, a desired dielectric constant can be obtained by containing 5.0% or more of the Nb 2 O 5 component. Therefore, the content of the Nb 2 O 5 component is preferably 5.0% or more, more preferably 7.0% or more, and still more preferably 10.0% or more.
On the other hand, when the content of the Nb 2 O 5 component is 40.0% or less, glass can be stably produced. Therefore, the content of the P 2 O 5 component is preferably 40.0% or less, more preferably 38.0% or less, and even more preferably 35.0% or less.
　本発明のガラス誘電体では、モル和（ＴｉＯ2＋Ｎｂ2Ｏ5）、すなわち、ＴｉＯ2の含有率（％）とＮｂ2Ｏ5の含有率（％）との合計が、２５．０％以上であることが好ましく、３０．０％以上であることがより好ましく、３５．０％以上であることがさらに好ましい。また、この合計が７０．０％以下であることが好ましく、６０．０％以下であることがより好ましく、５８．０％以下であることがさらに好ましい。この合計量は高すぎるとガラスの安定性が低下しやすくなる傾向があり、逆に低すぎると誘電率が低くなる傾向がある。 In the glass dielectric of the present invention, the molar sum (TiO 2 + Nb 2 O 5 ), that is, the total of the content (%) of TiO 2 and the content (%) of Nb 2 O 5 is 25.0% or more. Preferably, it is 30.0% or more, more preferably 35.0% or more. Further, the total is preferably 70.0% or less, more preferably 60.0% or less, and further preferably 58.0% or less. If this total amount is too high, the stability of the glass tends to decrease, and conversely, if it is too low, the dielectric constant tends to decrease.
　ＢａＯ成分とＺｎＯ成分との合計量（ＢａＯ＋ＺｎＯ）を５０．０％以下にすることでガラスの安定性及び誘電特性が低下しにくくなるのでＢａＯ成分とＺｎＯ成分の合計量は好ましくは５０．０％、より好ましくは４０．０％、最も好ましくは３７．０％を上限とする。一方、ＢａＯ成分及びＺｎＯ成分の合計量を３．０％以上にすることでガラスの安定性及び誘電特性が向上するので、その合計量は、好ましくは３．０％、より好ましくは５．０％、より好ましくは７．０％、最も好ましくは９．０％を下限とする。 By making the total amount of BaO component and ZnO component (BaO + ZnO) 50.0% or less, the stability and dielectric properties of the glass are hardly deteriorated, so the total amount of BaO component and ZnO component is preferably 50.0%. More preferably, the upper limit is 40.0%, and most preferably 37.0%. On the other hand, since the stability and dielectric properties of the glass are improved by setting the total amount of the BaO component and the ZnO component to 3.0% or more, the total amount is preferably 3.0%, more preferably 5.0. %, More preferably 7.0%, and most preferably 9.0%.
　本発明のガラスは、Ｎｂ2Ｏ5成分、ＴｉＯ2成分およびＢａＯ成分のモル和（Ｎｂ2Ｏ5成分＋ＴｉＯ2成分＋ＢａＯ成分）が３５．０％以上であることが好ましく、３８．０％以上であることがより好ましく、４０．０％以上であることがさらに好ましい。この合計量（モル和）が低すぎると誘電率が低くなる傾向がある。
　また、この合計量（モル和）は８０．０％以下であることが好ましく、６８．０％以下であることがより好ましく、６５．０％以下であることがさらに好ましい。この合計量（モル和）は高すぎるとガラスの安定性が低下しやすくなる傾向がある。 In the glass of the present invention, the molar sum of Nb 2 O 5 component, TiO 2 component and BaO component (Nb 2 O 5 component + TiO 2 component + BaO component) is preferably 35.0% or more, and 38.0% or more. It is more preferable that it is 40.0% or more. When this total amount (mol sum) is too low, the dielectric constant tends to be low.
The total amount (mole sum) is preferably 80.0% or less, more preferably 68.0% or less, and further preferably 65.0% or less. When this total amount (mole sum) is too high, the stability of the glass tends to decrease.
　ＳｉＯ2成分は、ガラスの安定性を高める効果があり、本発明のガラス誘電体における任意成分である。具体的な含有率は２０．０％以下であることが好ましく、１０．０％以下であることがより好ましく、５．０％以下であることがさらに好ましい。この成分含有率が高すぎるとガラスの安定性が低下しやすくなる。 The SiO 2 component has an effect of increasing the stability of the glass and is an optional component in the glass dielectric of the present invention. The specific content is preferably 20.0% or less, more preferably 10.0% or less, and even more preferably 5.0% or less. If this component content is too high, the stability of the glass tends to decrease.
　Ｂ2Ｏ3成分は、ガラスの安定性を高める効果があり、本発明のガラス誘電体における任意成分である。具体的な含有率は２０．０％以下であることが好ましく、１０．０％以下であることがより好ましく、７．０％以下であることがより好ましく、５．０％以下であることがさらに好ましい。この成分含有率が高すぎるとガラスの安定性が低下しやすくなる。 The B 2 O 3 component has an effect of increasing the stability of the glass and is an optional component in the glass dielectric of the present invention. The specific content is preferably 20.0% or less, more preferably 10.0% or less, more preferably 7.0% or less, and 5.0% or less. Further preferred. If this component content is too high, the stability of the glass tends to decrease.
　Ａｌ2Ｏ3成分は、ガラスの安定性を高める効果があり、本発明のガラス誘電体における任意成分である。具体的な含有率は１０．０％以下であることが好ましく、８．０％以下がより好ましく、５．０％以下であることがさらに好ましい。この成分含有率が高すぎるとガラスの安定性が低下しやすくなる。 The Al 2 O 3 component has an effect of increasing the stability of the glass and is an optional component in the glass dielectric of the present invention. The specific content is preferably 10.0% or less, more preferably 8.0% or less, and even more preferably 5.0% or less. If this component content is too high, the stability of the glass tends to decrease.
　ＺｎＯ成分は、ガラスの溶融性、安定性及び誘電率を高める効果があり、本発明のガラス誘電体に任意に添加できる成分である。従って、好ましくは０％超、より好ましくは１．０％以上、さらに好ましくは３．０％以上含有してもよい。他方で、この成分の含有率が高すぎるとガラスの安定性が低下しやすくなる傾向があるので、３０．０％以下含有することが好ましく、２８．０％以下含有することがより好ましく、２５．０％以下含有することがさらに好ましい。 The ZnO component has an effect of increasing the meltability, stability and dielectric constant of glass, and is a component that can be arbitrarily added to the glass dielectric of the present invention. Therefore, it may be contained preferably in an amount exceeding 0%, more preferably 1.0% or more, and further preferably 3.0% or more. On the other hand, if the content of this component is too high, the stability of the glass tends to decrease. Therefore, the content is preferably 30.0% or less, more preferably 28.0% or less, 25 More preferably, the content is 0.0% or less.
　ＢａＯ成分はガラスの溶融性、安定性及び誘電率を高める効果があり、本発明のガラス誘電体に任意に添加できる成分である。従って、好ましくは０％超、より好ましくは５．０％以上、さらに好ましくは１０．０％以上含有してもよい。他方で、この成分が高すぎると、ガラスの安定性が低下しやすくなるため、好ましくは３０．０％以下、より好ましくは２８．０％以下、さらに好ましくは２５．０％以下とする。 The BaO component has an effect of increasing the meltability, stability, and dielectric constant of glass, and is a component that can be arbitrarily added to the glass dielectric of the present invention. Therefore, it may be contained more preferably than 0%, more preferably 5.0% or more, and still more preferably 10.0% or more. On the other hand, if this component is too high, the stability of the glass tends to decrease, so it is preferably 30.0% or less, more preferably 28.0% or less, and even more preferably 25.0% or less.
　ＳｒＯ成分は、ガラスの溶融性、安定性及び誘電率を高める効果があり、本発明のガラス誘電体に任意に添加できる成分である。この成分の含有率が高すぎるとガラスの安定性が低下しやすくなる傾向があるので、３０．０％以下含有することが好ましく、２５．０％以下含有することがより好ましく、２０．０％以下含有することがさらに好ましい。 The SrO component has an effect of increasing the meltability, stability, and dielectric constant of glass, and is a component that can be arbitrarily added to the glass dielectric of the present invention. If the content of this component is too high, the stability of the glass tends to decrease. Therefore, the content is preferably 30.0% or less, more preferably 25.0% or less, and more preferably 20.0%. More preferably, it is contained below.
　ＣａＯ成分は、ガラスの溶融性と安定性を高める効果があり、本発明のガラス誘電体に任意に添加できる成分である。この成分の含有率が高すぎるとガラスの安定性が低下しやすくなる傾向があるので、３０．０％以下含有することが好ましく、２５．０％以下含有することがより好ましく、２０．０％以下含有することがさらに好ましい。 The CaO component has an effect of enhancing the meltability and stability of the glass, and can be optionally added to the glass dielectric of the present invention. If the content of this component is too high, the stability of the glass tends to decrease. Therefore, the content is preferably 30.0% or less, more preferably 25.0% or less, and more preferably 20.0%. More preferably, it is contained below.
　ＭｇＯ成分は、ガラスの溶融性と安定性を高める効果があり、本発明のガラス誘電体に任意に添加できる成分である。この成分の含有率が高すぎるとガラスの安定性が低下しやすくなる傾向があるので、３０．０％以下含有することが好ましく、２０．０％以下含有することがより好ましく、１５．０％以下含有することがさらに好ましい。 The MgO component has an effect of improving the meltability and stability of the glass, and can be optionally added to the glass dielectric of the present invention. If the content of this component is too high, the stability of the glass tends to decrease. Therefore, the content is preferably 30.0% or less, more preferably 20.0% or less, and more preferably 15.0%. More preferably, it is contained below.
　本発明のガラス誘電体は、酸化物換算組成の全物質量に対して、モル％で、ＲＯ成分（式中、ＲはＭｇ、Ｃａ、Ｓｒ、Ｂａからなる群より選択される１種以上）のモル和が５０．０％以下であることが好ましく、４０．０％以下であることがより好ましく、３７．０％以下であることがさらに好ましい。ＲＯ成分の含有率が上記のような範囲であると、ガラスの安定性及び誘電特性が向上する傾向がある。 The glass dielectric of the present invention is an RO component (in the formula, R is one or more selected from the group consisting of Mg, Ca, Sr, and Ba) with respect to the total amount of the oxide-converted composition. Is preferably 50.0% or less, more preferably 40.0% or less, and even more preferably 37.0% or less. When the content of the RO component is in the above range, the stability and dielectric properties of the glass tend to be improved.
　Ｌｉ2Ｏ成分は、ガラスの安定性を高める効果があり、本発明のガラス誘電体における任意成分である。具体的な含有率は１０．０％以下であることが好ましく、５．０％以下であることがより好ましく、３．０％以下であることがさらに好ましい。この成分含有率が高すぎるとガラスの絶縁破壊強度が低下しやすくなる。 The Li 2 O component has an effect of increasing the stability of the glass and is an optional component in the glass dielectric of the present invention. The specific content is preferably 10.0% or less, more preferably 5.0% or less, and further preferably 3.0% or less. If this component content is too high, the dielectric breakdown strength of the glass tends to decrease.
　Ｎａ2Ｏ成分は、ガラスの安定性を高める効果があり、本発明のガラス誘電体における任意成分である。具体的な含有率は１０．０％以下であることが好ましく、５．０％以下であることがより好ましく、３．０％以下であることがさらに好ましい。この成分含有率が高すぎるとガラスの絶縁破壊強度が低下しやすくなる。 The Na 2 O component has an effect of increasing the stability of the glass and is an optional component in the glass dielectric of the present invention. The specific content is preferably 10.0% or less, more preferably 5.0% or less, and further preferably 3.0% or less. If this component content is too high, the dielectric breakdown strength of the glass tends to decrease.
　Ｋ2Ｏ成分は、ガラスの安定性を高める効果があり、本発明のガラス誘電体における任意成分である。具体的な含有率は１５．０％以下であることが好ましく、８．０％以下であることがより好ましく、５．０％以下であることがさらに好ましい。この成分含有率が高すぎるとガラスの誘電率と絶縁破壊強度が低下しやすくなる。 The K 2 O component has an effect of increasing the stability of the glass and is an optional component in the glass dielectric of the present invention. The specific content is preferably 15.0% or less, more preferably 8.0% or less, and even more preferably 5.0% or less. If this component content is too high, the dielectric constant and dielectric breakdown strength of the glass tend to decrease.
　本発明のガラス誘電体は、Ｒｎ2Ｏ成分（式中、ＲｎはＬｉ、Ｎａ、Ｋからなる群より選択される１種以上）の合計量が絶縁破壊強度を低下させないために１０．０％以下であることが好ましく、５．０％以下であることがより好ましく、３．０％以下であることがさらに好ましく、含有しないことが最も好ましい。 The glass dielectric of the present invention is 10.0% because the total amount of the Rn 2 O component (wherein Rn is one or more selected from the group consisting of Li, Na and K) does not decrease the dielectric breakdown strength. Or less, more preferably 5.0% or less, still more preferably 3.0% or less, and most preferably not contained.
　本発明のガラスは、モル比（ＺｎＯ＋ＭｇＯ＋Ｒｎ2Ｏ）／（ＴｉＯ2＋Ｎｂ2Ｏ5）が０．７以下であることが好ましく、０．６５以下であることがより好ましく、０．６３以下であることがさらに好ましい。この成分含有率が高すぎると誘電特性が低下しやすい。 In the glass of the present invention, the molar ratio (ZnO + MgO + Rn 2 O) / (TiO 2 + Nb 2 O 5 ) is preferably 0.7 or less, more preferably 0.65 or less, and 0.63 or less. More preferably. If this component content is too high, the dielectric properties are likely to deteriorate.
　ＷＯ3成分は、ガラスの安定性及び誘電率の向上に効果があり、本発明のガラス誘電体における任意成分である。具体的な含有率は２０％以下であることが好ましく、１０．０％以下であることがより好ましく、８．０％以下であることがさらに好ましい。この成分含有率が高すぎるとガラスの安定性が低下しやすくなる。 The WO 3 component is effective in improving the stability and dielectric constant of glass, and is an optional component in the glass dielectric of the present invention. The specific content is preferably 20% or less, more preferably 10.0% or less, and even more preferably 8.0% or less. If this component content is too high, the stability of the glass tends to decrease.
　Ｔａ2Ｏ5成分は、ガラスの安定性及び誘電率の向上に効果あり、本発明のガラス誘電体における任意成分である。具体的な含有率は１５．０％以下であることが好ましく、１０．０％以下であることがより好ましく、５．０％以下であることがより好ましく、３．０％以下であることがさらに好ましい。この成分含有率が高すぎるとガラスの安定性が低下しやすくなる。 The Ta 2 O 5 component is effective in improving the stability and dielectric constant of glass, and is an optional component in the glass dielectric of the present invention. The specific content is preferably 15.0% or less, more preferably 10.0% or less, more preferably 5.0% or less, and 3.0% or less. Further preferred. If this component content is too high, the stability of the glass tends to decrease.
　ＺｒＯ2成分は、ガラスの安定性及び誘電率の向上に効果あるので本発明のガラス誘電体における任意成分である。具体的な含有率は１５．０％以下であることが好ましく、１０．０％以下であることがより好ましく、８．０％以下であることがより好ましく、５．０％以下であることがさらに好ましい。この成分含有率が高すぎるとガラスの安定性が低下しやすくなる。 The ZrO 2 component is an optional component in the glass dielectric of the present invention because it is effective in improving the stability and dielectric constant of the glass. The specific content is preferably 15.0% or less, more preferably 10.0% or less, more preferably 8.0% or less, and 5.0% or less. Further preferred. If this component content is too high, the stability of the glass tends to decrease.
　ＳｎＯ2成分は、誘電特性の改善に効果があるので、本発明のガラス誘電体における任意成分である。具体的な含有率は１０．０％以下であることが好ましく、５．０％以下であることがより好ましく、３．０％以下であることがさらに好ましい。この成分含有率が高すぎるとガラスの安定性が低下しやすくなる。 The SnO 2 component is an optional component in the glass dielectric of the present invention because it is effective in improving the dielectric properties. The specific content is preferably 10.0% or less, more preferably 5.0% or less, and further preferably 3.0% or less. If this component content is too high, the stability of the glass tends to decrease.
　Ｌｎ2Ｏ3成分（式中、ＬｎはＬａ、Ｃｅ、Ｇｄ、Ｙ、Ｄｙ、Ｙｂ、Ｌｕからなる群より選択される１種以上）は、誘電特性の改善に効果があり、本発明のガラス誘電体における任意成分である。これらの含有量（モル和）の合計が１０．０％以下であることが好ましく、５．０％以下であることがより好ましく、３．０％以下であることがさらに好ましい。これらの成分の含有率が高すぎるとガラスの安定性が低下しやすくなる。 The Ln 2 O 3 component (wherein Ln is at least one selected from the group consisting of La, Ce, Gd, Y, Dy, Yb, and Lu) is effective in improving dielectric properties, and the glass of the present invention It is an optional component in the dielectric. The total of these contents (mole sum) is preferably 10.0% or less, more preferably 5.0% or less, and even more preferably 3.0% or less. If the content of these components is too high, the stability of the glass tends to decrease.
　ＭxＯy成分（Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ａｇ、Ｍｏからなる群より選択される１種以上）は、誘電特性の改善に効果があり、本発明のガラス誘電体における任意成分である。これらの含有量（モル和）の合計が１０．０％以下であることが好ましく、５．０％以下であることがより好ましく、３．０％以下であることがより好ましく、１．０％以下であることがさらに好ましい。これらの成分の含有率が高すぎるとガラスの安定性が低下しやすくなる。 The M x O y component (one or more selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo) is effective in improving the dielectric properties, and the glass dielectric of the present invention. An optional ingredient in the body. The total of these contents (molar sum) is preferably 10.0% or less, more preferably 5.0% or less, more preferably 3.0% or less, and 1.0% More preferably, it is as follows. If the content of these components is too high, the stability of the glass tends to decrease.
　Ｆ成分はガラスの安定性を高めるので本発明のガラス誘電体における任意成分である。その含有率は、外割で３０．０％以下であることが好ましく、１５．０％以下であることがより好ましく、８．０％以下であることがさらに好ましい。この成分の含有率が高すぎると誘電特性及び絶縁破壊強度が低下しやすくなる。 The F component is an optional component in the glass dielectric of the present invention because it increases the stability of the glass. The content is preferably 30.0% or less, more preferably 15.0% or less, and even more preferably 8.0% or less. If the content of this component is too high, the dielectric properties and the dielectric breakdown strength tend to be reduced.
　Ｓｂ2Ｏ3成分は、ガラスの脱泡剤の効果があり、さらに誘電特性の改善に寄与するので、本発明のガラス誘電体における任意成分である。具体的な含有率は１０．０％以下であることが好ましく、５．０％以下であることがより好ましく、３．０％以下であることがより好ましく、１．０％以下であることがさらに好ましい。この成分含有率が高すぎるとガラスの安定性が低下しやすくなる。 The Sb 2 O 3 component is an optional component in the glass dielectric of the present invention because it has the effect of a glass defoamer and contributes to the improvement of the dielectric properties. The specific content is preferably 10.0% or less, more preferably 5.0% or less, more preferably 3.0% or less, and 1.0% or less. Further preferred. If this component content is too high, the stability of the glass tends to decrease.
　本発明のガラス誘電体は、１ｋＨｚにおける誘電率εが２０以上である。この誘電率εは２１以上であることが好ましく、２４以上であることがより好ましい。
　なお、本発明において、インピーダンスアナライザー（例えばソーラトロン社製　ＳＩ１２６０）を用いて１０Ｈｚから１ＭＨｚまでの周波数にわたって誘電率及び誘電損失を測定し、１ｋＨｚにおける値を本発明の誘電率及び誘電損失とした。 The glass dielectric of the present invention has a dielectric constant ε of 20 or more at 1 kHz. The dielectric constant ε is preferably 21 or more, and more preferably 24 or more.
In the present invention, the dielectric constant and dielectric loss were measured over a frequency range of 10 Hz to 1 MHz using an impedance analyzer (for example, SI1260 manufactured by Solartron), and the value at 1 kHz was defined as the dielectric constant and dielectric loss of the present invention.
＜用途＞
　本発明のガラス誘電体は、任意の形にすることが可能であるため、様々な誘電体として利用できる。例えば、通信機器や電子機器に搭載される回路基板及び電子部品、大容量高電圧コンデンサーなどの誘電材料に使用される。コンデンサーは電力変換装置における電流変動の緩衝、カップリングや平滑用に使用される。高電圧コンデンサーは半導体の加工や視力矯正手術で利用されるエキシマレーザー機器のほか、医療用Ｘ線装置、工業用高電圧電源や、再生可能エネルギー用送電システムに必要不可欠な部品である。これらのガラスは単独で上記の用途に用いられる以外に、繊維、粉末及びペーストなどの態様で他の誘電体と複合化した形でも使用されることも可能である。具体的には、基板上にパターン電極を形成された誘電体基板、積層基板材料、誘電体共振素子、誘電材料の焼成助剤、誘電体ペースト（誘電体粉末を有機化合物等からなるビヒクル中に懸濁させたものであって、通常、スクリーン印刷や打ち抜き型印刷により電極上に成膜されて使用される）等の用途が挙げられる。 <Application>
Since the glass dielectric of the present invention can be formed into an arbitrary shape, it can be used as various dielectrics. For example, it is used for dielectric materials such as circuit boards and electronic components, large-capacity high-voltage capacitors mounted on communication devices and electronic devices. The capacitor is used for current fluctuation buffering, coupling and smoothing in the power converter. High-voltage capacitors are indispensable components for excimer laser equipment used in semiconductor processing and vision correction surgery, medical X-ray equipment, industrial high-voltage power supplies, and renewable energy transmission systems. These glasses can be used in the form of being combined with other dielectrics in the form of fibers, powders, pastes, etc., in addition to being used alone for the above-mentioned purposes. Specifically, a dielectric substrate having a patterned electrode formed on the substrate, a laminated substrate material, a dielectric resonator element, a firing aid for the dielectric material, a dielectric paste (dielectric powder in a vehicle made of an organic compound, etc. The suspension is generally used after being formed on an electrode by screen printing or punching printing).
＜製造方法＞
　本発明のガラス誘電体は、通常のガラスを製造する方法であれば、特に限定されないが、例えば、以下の方法により製造することができる。各出発原料（酸化物、炭酸塩、硝酸塩、リン酸塩、硫酸塩など）を所定量秤量し、均一に混合する。混合した原料を石英坩堝、アルミナ坩堝または白金坩堝に投入し、溶解炉で１２００～１４５０℃の温度範囲にて１～１２時間溶解する。その後、攪拌、均質化した後、適当な温度に下げて金型等に鋳込み、ガラスを製造する。繊維状として使用される場合は、板状のガラスを再溶融し、ガラス繊維を得るが、最初の溶液から直接にガラス繊維を得てもよい。また、セラミックス誘電体の焼成助剤、フィラーとしてまたは誘電体ペーストとして使われる場合は、成形したバルクガラスを粉砕してもよく、また、最初の溶液から水に注いでカレットを得てその後粉砕してもよい。 <Manufacturing method>
Although the glass dielectric of this invention will not be specifically limited if it is a method of manufacturing normal glass, For example, it can manufacture by the following method. A predetermined amount of each starting material (oxide, carbonate, nitrate, phosphate, sulfate, etc.) is weighed and mixed uniformly. The mixed raw materials are put into a quartz crucible, an alumina crucible or a platinum crucible and melted in a melting furnace at a temperature range of 1200 to 1450 ° C. for 1 to 12 hours. Then, after stirring and homogenizing, it is lowered to an appropriate temperature and cast into a mold or the like to produce glass. When used as a fiber, the glass sheet is remelted to obtain glass fibers, but the glass fibers may be obtained directly from the initial solution. In addition, when used as a ceramic dielectric firing aid, filler or dielectric paste, the molded bulk glass may be crushed, or cullet is obtained by pouring water from the first solution into water. May be.
　以下、実施例によって本発明を更に具体的に説明するが、本発明はこれらによりなんら制限されるものではない。 Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples.
　（実施例１）
　組成：２５Ｐ2Ｏ5－１５ＴｉＯ2－２５Ｎｂ2Ｏ5－１５ＢａＯ－３ＳｒＯ－１０ＣａＯ－７ＺｎＯ　（モル％）
　上記の組成になるように原料（ＴｉＯ2、Ｎｂ2Ｏ5、Ｂａ（ＰＯ3）2、Ｓｒ（ＮＯ3）2、Ｃａ（ＰＯ3）2、ＺｎＯ）を調合し、よく混合した後、石英坩堝に入れて１２６０℃で１時間溶解した。その後、溶融液を白金坩堝に移し、さらに２時間溶解し、攪拌均質化してから溶融液を金型に流し込み、板状のガラスを得た。得られたガラスについて約３０ｍｍ×３０ｍｍ×１ｍｍに加工し、両面に金電極を蒸着してから、インピーダンスアナライザー（ソーラトロン社製　ＳＩ１２６０）により誘電特性を評価した。その結果を図１に示す。この図から、本組成のガラスの誘電率と誘電損失は共に周波数によって殆ど変化しなかったことがわかる。１ｋＨｚにおける誘電率εおよび誘電損失はそれぞれ２７と０．００４０であった。
　また、絶縁破壊強度は７９ｋＶ／ｍｍあった。なお、絶縁破壊強度は厚み１ｍｍのサンプルを用いて、JIS C 2141に準じて測定した。 Example 1
Composition: 25P 2 O 5 -15TiO 2 -25Nb 2 O 5 -15BaO-3SrO-10CaO-7ZnO (mol%)
The raw materials (TiO 2 , Nb 2 O 5 , Ba (PO 3 ) 2 , Sr (NO 3 ) 2 , Ca (PO 3 ) 2 , ZnO) were prepared and mixed well so as to have the above composition, and then quartz It put into the crucible and melt | dissolved at 1260 degreeC for 1 hour. Thereafter, the molten liquid was transferred to a platinum crucible, further melted for 2 hours, stirred and homogenized, and then poured into a mold to obtain a plate-like glass. The obtained glass was processed to about 30 mm × 30 mm × 1 mm, gold electrodes were vapor-deposited on both sides, and dielectric characteristics were evaluated by an impedance analyzer (SI1260 manufactured by Solartron). The result is shown in FIG. From this figure, it can be seen that the dielectric constant and dielectric loss of the glass of this composition hardly changed with frequency. The dielectric constant ε and dielectric loss at 1 kHz were 27 and 0.0040, respectively.
The dielectric breakdown strength was 79 kV / mm. The dielectric breakdown strength was measured according to JIS C 2141 using a sample having a thickness of 1 mm.
　実施例１と類似な方法で、実施例２～２５および比較例１を作製した。各実施例および比較例の組成および誘電特性を表１～４にまとめた。また、絶縁破壊強度を表５にまとめた。実施例１に比べて本発明のガラス誘電体は同程度の誘電率を有するが、誘電損失は一桁低く、さらに絶縁破壊強度は２倍以上高くなったことが分かる。 Examples 2 to 25 and Comparative Example 1 were produced in the same manner as in Example 1. The compositions and dielectric properties of the examples and comparative examples are summarized in Tables 1 to 4. The dielectric breakdown strength is summarized in Table 5. It can be seen that the glass dielectric of the present invention has the same dielectric constant as in Example 1, but the dielectric loss is an order of magnitude lower and the dielectric breakdown strength is more than doubled.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

Claims (6)

  1. 　酸化物換算組成の全物質量に対して、モル％で
    　Ｐ2Ｏ5成分　１５．０％～４０．０％、
    　ＴｉＯ2成分　１．０％～４０．０％、
    　Ｎｂ2Ｏ5成分　５．０％～４０．０％、
    　モル和（ＢａＯ＋ＺｎＯ）　３．０％～５０．０％
    を含有し、１ｋＨｚにおける誘電率が２０以上であることを特徴とするガラス誘電体。     P 2 O 5 component 15.0% to 40.0% in mol% with respect to the total amount of substances in oxide equivalent composition,
    TiO 2 component 1.0% to 40.0%,
    Nb 2 O 5 component 5.0% to 40.0%,
    Molar sum (BaO + ZnO) 3.0% to 50.0%
    And a dielectric constant at 1 kHz of 20 or more.
  2. 　酸化物換算組成の全物質量に対して、モル％で
    　ＳｉＯ2成分　０～２０．０％、
    　Ｂ2Ｏ3成分　０～２０．０％、
    　Ａｌ2Ｏ3成分　０～１０．０％、
    　ＺｎＯ成分　０～３０．０％、
    　ＢａＯ成分　０～３０．０％、
    　ＳｒＯ成分　０～３０．０％、
    　ＣａＯ成分　０～３０．０％、
    　ＭｇＯ成分　０～３０．０％、
    　Ｌｉ2Ｏ成分　０～１０．０％、
    　Ｎａ2Ｏ成分　０～１０．０％、
    　Ｋ2Ｏ成分　０～１５．０％、
    　ＷＯ3成分　０～２０．０％、
    　Ｔａ2Ｏ5成分　０～１５．０％
    　ＺｒＯ2成分　０～１５．０％
    　ＳｎＯ２成分　０～１０．０％、
    　Ｓｂ2Ｏ3成分　０～１０．０％、
    　外割でＦを０～３０．０％
    を含有することを特徴とする請求項１に記載のガラス誘電体。     SiO 2 component 0 to 20.0% in mol% with respect to the total amount of substances in oxide equivalent composition,
    B 2 O 3 component 0-20.0%,
    Al 2 O 3 component 0 to 10.0%,
    ZnO component 0-30.0%,
    BaO component 0-30.0%,
    SrO component 0-30.0%,
    CaO component 0-30.0%,
    MgO component 0-30.0%,
    Li 2 O component 0 to 10.0%,
    Na 2 O component 0 to 10.0%,
    K 2 O component 0 to 15.0%,
    WO 3 component 0-20.0%,
    Ta 2 O 5 component 0 ～ 15.0%
    ZrO 2 component 0 ～ 15.0%
    SnO 2 component 0-10.0%,
    Sb 2 O 3 component 0 to 10.0%,
    0% to 30.0% for F
    The glass dielectric according to claim 1, comprising:
  3. 　酸化物換算組成の全物質量に対して、モル％で
    　Ｌｎ2Ｏ3成分（式中、ＬｎはＬａ、Ｃｅ、Ｇｄ、Ｙ、Ｄｙ、Ｙｂ、Ｌｕからなる群より選択される１種以上）のモル和が１０．０％以下であり、
    　ＲＯ成分（式中、ＲはＭｇ、Ｃａ、Ｓｒ、Ｂａからなる群より選択される１種以上）のモル和が５０．０％以下であり、
    　Ｒｎ2Ｏ成分（式中、ＲｎはＬｉ、Ｎａ、Ｋからなる群より選択される１種以上）のモル和が１０．０％以下であり、
    　ＭxＯy成分（Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ａｇ、Ｍｏからなる群より選択される１種以上）のモル和が１０．０％以下である、請求項１または２に記載のガラス誘電体。     Ln 2 O 3 component in mol% with respect to the total amount of oxide-converted composition (wherein Ln is one or more selected from the group consisting of La, Ce, Gd, Y, Dy, Yb, and Lu) The molar sum of is 10.0% or less,
    The molar sum of the RO component (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, Ba) is 50.0% or less,
    The molar sum of the Rn 2 O component (wherein Rn is one or more selected from the group consisting of Li, Na and K) is 10.0% or less,
    The molar sum of M x O y components (one or more selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo) is 10.0% or less. 2. The glass dielectric according to 2.
  4. 　酸化物換算組成のＮｂ2Ｏ5成分、ＴｉＯ2成分およびＢａＯ成分のモル和（Ｎｂ2Ｏ5成分＋ＴｉＯ2成分＋ＢａＯ成分）が３５．０～８０．０％である、請求項１から３のいずれかに記載のガラス誘電体。 The molar sum of the Nb 2 O 5 component, the TiO 2 component and the BaO component (Nb 2 O 5 component + TiO 2 component + BaO component) having an oxide equivalent composition is 35.0 to 80.0%. The glass dielectric according to any one of the above.
  5. 　モル比（ＺｎＯ＋ＭｇＯ＋Ｒｎ2Ｏ）／（ＴｉＯ2＋Ｎｂ2Ｏ5）が０．７以下である、請求項１から４のいずれかに記載のガラス誘電体。 The glass dielectric according to claim 1, wherein a molar ratio (ZnO + MgO + Rn 2 O) / (TiO 2 + Nb 2 O 5 ) is 0.7 or less.
  6. 　モル和（ＴｉＯ2＋Ｎｂ2Ｏ5）が２５．０～７０．０％である、請求項１から５のいずれかに記載のガラス誘電体。 6. The glass dielectric according to claim 1, wherein a molar sum (TiO 2 + Nb 2 O 5 ) is 25.0 to 70.0%.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07118060A (en) * 1993-08-24 1995-05-09 Nippon Electric Glass Co Ltd High-dielectric constant glass ceramic
JP2002265234A (en) * 2001-03-08 2002-09-18 Asahi Glass Co Ltd Crystallized glass for optical filter substrate and optical filter
JP2003139948A (en) * 2002-10-22 2003-05-14 Ohara Inc Glass for optical filter and optical filter
JP2003212592A (en) * 2002-01-24 2003-07-30 Ohara Inc Glass having high dielectric constant and glass substrate
JP2011098869A (en) * 2009-11-07 2011-05-19 Ohara Inc Glass ceramic, method for manufacturing the same, photocatalytically functional compact and hydrophilic compact
JP2011116620A (en) * 2009-11-07 2011-06-16 Ohara Inc Composite and method for manufacturing the same, photocatalytic functional member, and hydrophilic member
JP2015166289A (en) * 2014-03-03 2015-09-24 株式会社オハラ glass or crystallized glass

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07118060A (en) * 1993-08-24 1995-05-09 Nippon Electric Glass Co Ltd High-dielectric constant glass ceramic
JP2002265234A (en) * 2001-03-08 2002-09-18 Asahi Glass Co Ltd Crystallized glass for optical filter substrate and optical filter
JP2003212592A (en) * 2002-01-24 2003-07-30 Ohara Inc Glass having high dielectric constant and glass substrate
JP2003139948A (en) * 2002-10-22 2003-05-14 Ohara Inc Glass for optical filter and optical filter
JP2011098869A (en) * 2009-11-07 2011-05-19 Ohara Inc Glass ceramic, method for manufacturing the same, photocatalytically functional compact and hydrophilic compact
JP2011116620A (en) * 2009-11-07 2011-06-16 Ohara Inc Composite and method for manufacturing the same, photocatalytic functional member, and hydrophilic member
JP2015166289A (en) * 2014-03-03 2015-09-24 株式会社オハラ glass or crystallized glass

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