Classifications

• • 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
  • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
• • 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
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
  • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay

Definitions

• the present invention relates to materials for manufacturing high-frequency dielectric ceramics, and in particular to materials that become high-frequency dielectric ceramics when fired at low temperatures, and high-frequency dielectric ceramics obtained by firing said materials at low temperatures.
• Alumina, crystallized glass ceramics, and other materials are known as dielectric materials useful in the manufacture of electronic circuits that utilize high frequencies (especially frequencies of 10 GHz or higher), and these are used as materials for circuit boards.
• materials for manufacturing dielectric ceramics are used that can be sintered at temperatures of around 800 to 1000°C, which is lower than but close to the melting point of the metal material, so that they can be fired simultaneously with the metal wiring material (Ag, Au, etc.).
• Patent Document 1 describes a material containing crystallized glass powder and alumina powder, etc.
• Patent Document 2 describes a material for manufacturing dielectric ceramics that contains MgO, SiO2 , and sintering aid components.
• the object of the present invention is to provide a dielectric ceramic that can be sintered at low temperatures of 800 to 1000°C and has a low dielectric constant and low dielectric tangent at 10 GHz, and materials for producing the same.
• the inventors have found that dielectric ceramics mainly containing SiO2 crystal phase and CaB2O4 crystal phase can be fired at a low temperature range of 800 to 1000°C, and have a low dielectric constant and low dielectric loss tangent. Furthermore, they have found that a dielectric ceramic with a particularly low dielectric constant and low dielectric loss tangent can be obtained by reducing the amount of CaSiO3 crystal phase in the dielectric ceramic, and have completed the present invention through further investigation. That is, the present invention provides the following materials for manufacturing high frequency dielectric ceramics, uses thereof, high frequency dielectric ceramics, and manufacturing methods thereof.
• a material for manufacturing high-frequency dielectric ceramics The composition of the porcelain formed by firing at a temperature in the range of 800 to 1000 ° C. is 42 to 75% SiO2 , expressed in mass % in terms of oxide. B2O3 15-40 % and CaO 5-32%; A material comprising an inorganic oxide powder in a ratio that will contain a glass powder and a non-softening filler powder. 2.
• the composition of the glass powder is, in terms of oxide mass%, 0 to 35% SiO2 ; B2O3 25-75% and CaO 20-50% ;
• the composition of the porcelain formed by the firing is, in terms of mass% of oxide, 42 to 62% SiO2 ; B2O3 15-40% and CaO 10-32% ; 3.
• the material according to claim 1 or 2 comprising an inorganic oxide powder in a ratio that results in the material being contained in the inorganic oxide powder.
• the inorganic oxide powder comprises silica powder.
• Any of the materials 1 to 4 above, in which the content of Al 2 O 3 in the composition of the porcelain formed by firing is less than 5 mass %.
• Any of the materials 1 to 5 above, wherein the content of alkali metal oxides in the composition of the porcelain formed by firing is less than 2 mass %. 7.
• High-frequency dielectric ceramic The composition, expressed in mass% in terms of oxide, is 42 to 75% SiO2 , B2O3 15-40 % and CaO 5-32%; It contains porcelain. 12.
• a method for producing porcelain comprising the steps of providing a material comprising an inorganic oxide powder and firing the material,
• the composition of the porcelain formed by firing is, in terms of mass % of oxide, 42 to 75% SiO2 , B2O3 15-40 % and CaO 5-32%;
• the inorganic oxide powder is prepared so as to contain a glass powder and a non-softening filler powder,
• the method is characterized in that the material is sintered at a temperature in the range of 800 to 1000°C. 14.
• the composition of the glass powder is, in terms of oxide mass%, 0 to 35% SiO2 ; B2O3 25-75% and CaO 20-50% ; 14.
• the composition of the porcelain formed by the firing is, in terms of mass% of oxide, 42 to 62% SiO2 ; B2O3 15-40% and CaO 10-32% ; 14.
• a use of a material comprising an inorganic oxide powder for producing a ceramic having a relative dielectric constant of 4.0 to 6.0 and a dielectric loss tangent of 0.0001 to 0.0020 at 17.10 GHz by firing comprising:
• the composition of the porcelain formed by firing is, in terms of mass % of oxide, 42 to 75% SiO2 , B2O3 15-40 % and CaO 5-32%;
• the material is prepared to contain, and the inorganic oxide powder comprises a glass powder and a non-softening filler powder.
• the composition of the glass powder, expressed in mass% in terms of oxide, is 0 to 35% SiO2 ; B2O3 25-75% and CaO 20-50% ; 18.
• composition of the porcelain formed by firing is, in terms of mass % of oxide, 42 to 62% SiO2 , B2O3 15-40% and CaO 10-32% ; 4.
• the material for manufacturing high frequency dielectric ceramics of the present invention can be sintered at a relatively low temperature of 800-1000°C to produce high frequency dielectric ceramics with low dielectric constant and low dielectric tangent properties suitable for use at high frequencies, and it is possible to provide such high frequency dielectric ceramics.
• the material of the present invention can be used to manufacture high frequency circuits using the dielectric ceramic sheet obtained by firing as a substrate, and in particular, since it is a material that can be fired at temperatures within the range of 800-1000°C, when used to manufacture printed circuit boards, it can be fired simultaneously with conductors such as Ag and Au printed on the surface of the material formed into a sheet, making it possible to manufacture high frequency laminated boards by simultaneous firing.
• the composition of the raw glass material or the porcelain obtained by firing when expressing the composition of the raw glass material or the porcelain obtained by firing, for convenience, it is expressed as a combination of elemental oxides of a single element, and the content of each elemental oxide is expressed as its mass % in the raw glass or porcelain.
• the material for manufacturing high frequency dielectric ceramics of the present invention may have a composition as a whole that becomes ceramics of the composition specified in the present invention by firing.
• raw materials include inorganic oxides (e.g., SiO 2 , B 2 O 3 , CaO), carbonates (e.g., calcium carbonate CaCO 3 ) that become inorganic oxides by degassing by firing, and hydroxides (e.g., boric acid H 3 BO 3 (also written as B(OH) 3 )), and the raw materials may be amorphous (glass) or crystalline.
• a part of the raw materials is amorphous (e.g., glass containing B 2 O 3 and B 2 O 3 , or glass further containing SiO 2 ).
• a part of the raw materials is silica (SiO 2 ), which may be amorphous or crystalline (quartz, ⁇ -quartz at normal temperature and normal pressure).
• the amorphous silica in the material for manufacturing high frequency dielectric ceramics of the present invention is in the form of ⁇ -quartz in the ceramics obtained by firing.
• the material for manufacturing high frequency dielectric ceramics of the present invention may be in the form of the above-mentioned powder mixture, or may be in the form of a semi-liquid such as a paste, slurry, or green sheet in which the powder mixture is mixed with an additive that can be removed during firing, such as an organic binder (e.g., polyvinyl butyral or acrylic resin) or an organic solvent (e.g., alcohols, ketones, toluene).
• an organic binder e.g., polyvinyl butyral or acrylic resin
• an organic solvent e.g., alcohols, ketones, toluene
• the material for manufacturing high frequency dielectric ceramics of the present invention becomes ceramics when fired, and the composition of the resulting ceramics is preferably 42 to 75% SiO2 , expressed in mass % in terms of oxides.
• the material for manufacturing high frequency dielectric ceramics of the present invention can be obtained by mixing the raw materials so that the ratios of SiO 2 , B 2 O 3 , and CaO in the composition of the ceramic formed by firing are within these ranges. By firing this at 800 to 1000° C., it is possible to obtain a dielectric ceramic that mainly contains SiO 2 phase and CaB 2 O 4 phase, has a relative dielectric constant of 6.0 or less, and a dielectric loss tangent of 0.0001 to 0.0020.
• SiO 2 is the main component of the ceramic.
• the SiO 2 content is preferably 42% or more, more preferably 47% or more, and even more preferably 49% or more, from the viewpoint of lowering the dielectric constant and dielectric dissipation factor of the ceramic.
• the SiO 2 content is preferably 75% or less, more preferably 72% or less, and even more preferably 70% or less. For example, it can be 62% or less, or 58% or less, or even 54% or less.
• B 2 O 3 is the main component of the ceramic.
• the content of B 2 O 3 is preferably 15% or more, more preferably 19% or more, and even more preferably 25% or more, from the viewpoint of lowering the dielectric constant and dielectric dissipation factor of the ceramic and enabling the sintering of the ceramic manufacturing material at 800 to 1000°C.
• the content of B 2 O 3 is preferably 40% or less, more preferably 36% or less, and even more preferably 34% or less.
• CaO is the main component of the ceramic.
• the CaO content is preferably 5% or more, more preferably 6% or more, and even more preferably 7% or more. For example, it can be 10% or more, or 12% or more, or even 14% or more.
• the CaO content is preferably 35% or less, more preferably 32% or less, and even more preferably 30% or less. For example, it can be 25% or less.
• the high frequency dielectric ceramic of the present invention may contain oxides of other elements as optional components by including them in the material, as long as the characteristics of low dielectric constant and low dielectric tangent are not impaired.
• MgO and ZnO play a role similar to that of CaO as the main component of high frequency dielectric ceramics, and can be used to adjust the sinterability and thermal expansion coefficient.
• MgO is preferably less than 10%, more preferably less than 5%, even more preferably less than 3%, even more preferably less than 2%, and especially preferably less than 1%.
• ZnO is preferably less than 10%, more preferably less than 5%, even more preferably less than 2%, and especially preferably less than 1%.
• the total content of SiO 2 , B 2 O 3 , CaO, MgO, and ZnO in the composition of the ceramic obtained after firing is preferably 95% or more, more preferably 97% or more, and even more preferably 99% or more.
• the content is preferably less than 5%, more preferably less than 2%, even more preferably less than 1%, and particularly preferably less than 0.1%.
• alkali metal oxides Li 2 O, Na 2 O, K 2 O, etc.
• their total content is preferably less than 5%, more preferably less than 2%, even more preferably less than 1% (e.g., both less than 0.5%), and particularly preferably less than 0.1%.
• the mass percentage ratio CaO/ B2O3 is preferably 2 or less, more preferably 1.3 or less, and even more preferably 0.81 or less.
• the most preferable content of components in the high frequency dielectric ceramic of the present invention is: SiO2 49-54%, B2O3 25-34% , CaO 14 to 25%, It is.
• the material for manufacturing dielectric ceramics of the present invention can be of any type of powder, so long as it can produce ceramics of the desired composition after firing.
• metal wiring materials such as Ag and Au
• composition of such glass material powder that softens during firing is, expressed in mass % in terms of oxide, 0 to 35% SiO2 , B2O3 25-75% , CaO 20 to 50%, It is preferable that it contains
• a filler material powder that does not soften when fired at 800 to 1000°C is called a "non-softening filler".
• the non-softening filler material powder one or more of high melting point crystalline substances such as quartz and amorphous silica, and CaO-B 2 O 3 -SiO 2 type glasses having a relatively high softening point and a composition that does not soften when fired at the above temperature range (non-softening) can be used.
• the non-softening filler material powder silica (amorphous or crystalline) powder is more preferable, and ⁇ -quartz powder is particularly preferable.
• the mixing ratio thereof, expressed in mass % is preferably 35-95% softening glass material powder and 5-65% non-softening filler, more preferably 35-90% softening glass material powder and 10-65% non-softening filler, even more preferably 40-90% softening glass material powder and 10-60% non-softening filler, and particularly preferably 45-75% softening glass material powder and 25-55% non-softening filler.
• the 50% particle size (D 50 ) based on volume may be 0.1 to 10 ⁇ m.
• D 50 is the particle size at which the cumulative amount counted from the small particle size side in the volume-based particle size distribution is 50% of the entire sample, and can be obtained by particle size distribution measurement based on the laser diffraction/scattering method.
• An example of a measuring device based on this method is a laser diffraction/scattering type particle size distribution measuring device (model name "MT-3300", manufactured by Nikkiso Co., Ltd.), but the measuring device is not limited to this as long as it can perform measurements based on this method.
• the material for manufacturing high frequency dielectric ceramics of the present invention can be used to manufacture dielectric resonators and the like by known methods.
• the powder of the material for manufacturing high frequency dielectric ceramics can be compressed and molded, and then fired at a temperature of 800 to 1000°C to obtain dielectric ceramics.
• the dimensions of the obtained dielectric ceramics can be adjusted by cutting or other processes.
• the obtained dielectric ceramics can be metal-plated or coated with metal paste and fired to form electrodes.
• a laminated substrate by forming the material for manufacturing high frequency dielectric ceramics of the present invention into multiple sheets, forming vias (through holes) corresponding to each part of the circuit in each of them, metal plating, coating with metal paste, etc., stacking them, pressurizing them together, and simultaneously firing them at a temperature of 800 to 1000°C.
• the material for manufacturing high frequency dielectric ceramics of the present invention can be used to manufacture laminated substrates by known methods.
• a laminated substrate can be obtained by forming green sheets using a doctor blade method or the like, printing conductive paste on the sheet surfaces, laminating and pressing the sheets, and then firing at a temperature of 800 to 1000°C.
• dielectric properties dielectric constant, dielectric loss tangent
• the above-mentioned material powder was mixed with the organic binder as described above, molded, and then fired at 900°C or 1000°C for 1 hour to obtain a sintered body of about 1.5 mm x about 1.5 mm x about 50 mm. This was used as a sample for measuring dielectric properties.
• the dielectric properties were measured by measuring the relative permittivity and dielectric loss tangent at 10 GHz using a cavity resonator method (IEC 62562: 2010).
• the cavity resonator used was a CP531 (resonance mode: TM 020 ) manufactured by Kanto Electronics Application Development Co., Ltd.
• compositions and evaluation results of the examples are shown in Tables 1 to 5.
• the ceramics of Examples 8 to 12 were obtained by firing at 900°C, Example 13 at 800°C, and Examples 14 and 15 at 1000°C.
• the types of crystal phases identified in each of the ceramics were similar to those of Examples 1 to 7, and therefore it was determined that the ceramics exhibited dielectric properties equivalent to those of the ceramics of Examples 1 to 7.
• the material for manufacturing dielectric ceramics of the present invention is useful for producing dielectric ceramics having a low dielectric constant and low dielectric loss for use in high frequency bands of 10 GHz or more.

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• Compositions Of Oxide Ceramics (AREA)

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• 2024
  • 2024-03-20 JP JP2025508589A patent/JPWO2024195810A1/ja active Pending
  • 2024-03-20 WO PCT/JP2024/010878 patent/WO2024195810A1/ja not_active Ceased
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