CN1791562A - Dielectric ceramic composition, process for producing the same, dielectric ceramic employing it and multilayer ceramic component - Google Patents

Abstract

The present invention discloses laminated ceramic components with a relative permittivity _εr of 15-25 enabling the formation of low resistance conductors of suitable dimensions below 800°C that can be encapsulated and laminated with Cu or Ag by simultaneous sintering. It is sintered at a temperature of -1000°C, and has low dielectric loss tanδ (high Q value), and the absolute value of the temperature coefficient τ _f of the resonance frequency is not greater than 50ppm/°C. The dielectric ceramic composition is based on 100 parts by weight of the main component of the general formula x'Zn ₂ TiO ₄ -(1-x'-y')ZnTiO ₃ -y'TiO ₂ , wherein 0.15<x'<0.8 and 0≤ y'≤0.2, containing 3-30 parts by weight of lead-free low-melting point glass, the low-melting point glass contains 50-75% by weight of ZnO, 5-30% by weight of B ₂ O ₃ , and 6-15% by weight of SiO ₂ , 0.5-5% by weight of Al ₂ O ₃ , and 3-10% by weight of BaO.

Description

Dielectric ceramic composition, method for producing same, dielectric ceramic and laminated ceramic part using same

technical field

The invention relates to a dielectric ceramic with a relative permittivity of about 15-25 and a smaller absolute value of the temperature coefficient τ _f of the resonant frequency. The dielectric ceramic can be sintered with Au, Ag, Cu, etc. at the same time as a low-resistance conductor, and has Low dielectric loss (high Q) for laminated ceramic components, and relates to compositions for obtaining said dielectric ceramics, methods for manufacturing said dielectric ceramic compositions, and lamination using said dielectric ceramic compositions Ceramic components such as laminated dielectric capacitors, LC filters and the like.

In particular, the present invention relates to a dielectric ceramic composition comprising a main component containing Zn ₂ TiO ₄ and ZnTiO ₃ and, if necessary, TiO ₂ , and a glass component, and to a method for producing the dielectric ceramic composition, and a dielectric ceramic and a laminated ceramic part using the dielectric ceramic composition; and further relates to a dielectric ceramic composition comprising a main component and a glass component, wherein the main component contains Zn ₂ TiO ₄ , ZnTiO ₃ and Al ₂ O ₃ And if necessary, it further contains TiO ₂ , its production method, and dielectric ceramics and laminated ceramic parts using the dielectric ceramic composition.

Background technique

In recent years, the development of microwave circuit integration has put forward the requirements of small size, small dielectric loss (tanδ) and stable dielectric properties for dielectric resonators. The market for laminated chip components with internally laminated electrode conductors for dielectric resonator components is therefore growing rapidly. The inner conductors of the laminated chip components use noble metals such as Au, Pt, Pd, and the like. However, from the viewpoint of cost saving, the above-mentioned conductor material has been replaced by Ag or Cu or an alloy containing Ag or Cu as a main component which is relatively cheaper than the above-mentioned conductor material. In particular, Ag or an alloy containing Ag as a main component has low resistance to direct current and is advantageous for improving the Q characteristic of a dielectric resonator or the like, and thus there is a strong demand for it. However, Ag or an alloy containing Ag as a main component has a low melting point of about 960° C., and a dielectric material capable of sintering at a temperature lower than the melting point is required.

In the case of using a dielectric resonator to form a dielectric filter, the characteristics required for the dielectric material are: (1) The absolute value of the temperature coefficient τ _f of the resonant frequency of the dielectric material is small, thereby reducing the temperature caused by the temperature as much as possible. (2) The Q value of the dielectric material is high, so as to reduce the insertion loss as much as possible as required for the dielectric filter. In addition, in the vicinity of microwaves used in cellular phones, etc., the length of the resonator is limited by the relative permittivity ε _r of the dielectric material. Therefore, a dielectric material is required to have a high relative permittivity ε _r in order to miniaturize an element. In this case, the resonator length is determined according to the wavelength of the electromagnetic wave used. The wavelength λ of an electromagnetic wave propagating through a dielectric material with a relative permittivity ε _r is represented by λ=λ ₀ /(ε _r ) ^1/2 , where λ ₀ is the wavelength of an electromagnetic wave propagating through a vacuum.

Therefore, by increasing the dielectric constant of the dielectric material used, the components can be miniaturized. However, if the component is too small, the required processing accuracy is extremely strict. As a result, the actual machining accuracy tends to deteriorate and is easily affected by the printing accuracy of the electrodes. For some purposes, it is desired that the relative permittivity ε _r be in a suitable range (eg about 10-40 or more preferably about 15-25) so that the components are not too small.

In order to meet these requirements, the known dielectric material that can prepare dielectric elements at a temperature not higher than 1000 ° C can be a material in which inorganic dielectric particles are dispersed in a resin (JP (A)-6-132621), composed of BaO-TiO ₂ - Glass ceramics composed of composite materials of _{Nd 2} O ₃ -based ceramics and glass (JP(A)-10-330161, page 3, paragraph [0005] and Table 1), etc. Also known is a dielectric ceramic containing TiO ₂ and ZnO and further containing a B ₂ O ₃ -based glass (JP(B)-3103296).

However, the element disclosed in JP(A)-6-132621 has an allowable upper temperature limit of about 400°C, which poses a problem that multilayering and fine wiring cannot be performed by simultaneous sintering with Ag or the like used as a wiring conductor.

The glass-ceramic material disclosed in JP(A)-10-330161 has the following problems. The relative permittivity ε _r of this material is greater than 40, thus making the component too small. As a result, the required processing accuracy is too strict, so that the actual processing accuracy deteriorates, and it is easily affected by the printing accuracy of the electrodes.

In addition, the composition disclosed in JP(B)-3103296 has a relative dielectric constant as high as about 25-70, as can be seen from the examples thereof. The temperature coefficient of the dielectric properties varies greatly depending on the composition, so that its absolute value exceeds 700 ppm/°C in some cases. In order to obtain a dielectric component for high frequency, the above-mentioned material is required to have a suitable relative permittivity, a small dependence of dielectric properties on temperature, and a high Q value.

In addition, the dielectric properties of the dielectric ceramic obtained by sintering the dielectric ceramic composition usually change or have differences due to changes in sintering temperature and composition. Such characteristic changes and differences due to changes in sintering temperature and composition cause deterioration in yield in mass production.

Contents of the invention

The object of the present invention is to provide dielectric ceramics with a relative permittivity of about 10-40, more preferably about 15-25, so that laminated ceramic parts etc. Temperature sintering, sintering at this temperature enables low-resistance conductors such as Cu, Ag, etc. to be encapsulated and multilayered based on simultaneous sintering, the dielectric ceramic has a small dielectric loss tanδ (high Q value), and The absolute value of the temperature coefficient τ _f of its resonance frequency is 50 ppm/°C or less, and to provide a dielectric ceramic composition capable of obtaining the above-mentioned dielectric ceramic, or in particular to provide a small characteristic change and variation caused by a change in sintering temperature, and A dielectric ceramic composition with less composition change during sintering, and a method for manufacturing the dielectric ceramic composition. Another object of the present invention is to provide a laminated ceramic part having a dielectric layer and an internal electrode made of such as the above-mentioned dielectric ceramic, the internal electrode containing Cu or Ag as a main component, such as a laminated ceramic capacitor or LC filter.

(1) The first embodiment of the present invention

In order to solve the above-mentioned problems, the present inventors conducted intensive studies and found the following results. That is, if a glass containing at least ZnO, B ₂ O ₃ , SiO ₂ , Al ₂ O ₃ and BaO is added to a mixture containing ZnTiO ₃ and Zn ₂ TiO ₄ and, if necessary, TiO ₂ , 15- ε _r in the range of 25 and small dielectric loss tanδ (high Q value), and the formation ratio between ZnTiO ₃ , Zn ₂ TiO ₄ and TiO ₂ does not change even after sintering at 800-1000°C. With glass containing ZnO, dissolution of ZnO components from ZnTiO ₃ and Zn ₂ TiO ₄ into the glass can be suppressed as much as possible, so that changes in dielectric properties caused by composition changes can be suppressed. Thus, using Cu, Ag, etc. as a wiring conductor enables lamination and fine pattern wiring.

The present invention relates to a dielectric ceramic composition comprising 100 parts by weight of a main component represented by the general formula x'Zn ₂ TiO ₄ -(1-x'-y')ZnTiO ₃ -y'TiO ₂ , wherein x' Satisfy 0.15<x'<0.8, y' satisfies 0≤y'≤0.2; and contains 3-30 parts by weight of lead-free low-melting glass, the lead-free low-melting glass contains 50-75% by weight of ZnO, 5 - 30% by weight of B ₂ O ₃ , 6-15% by weight of SiO ₂ , 0.5-5% by weight of Al ₂ O ₃ , and 3-10% by weight of BaO.

The present invention also relates to a dielectric ceramic containing Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ crystalline phases (wherein the TiO ₂ phase can be omitted, the following conditions are also applicable) and a glass phase, said dielectric ceramic is obtained by sintering a dielectric ceramic composition .

In addition, the present invention relates to a method for producing a dielectric ceramic composition, _which includes the steps _{of :} mixing ZnO raw _material powder and TiO ₂ raw material powder, and _calcining them to obtain A ceramic powder whose content may be 0); the resulting ceramic powder is mixed with lead-free low-melting glass containing 50-75% by weight of ZnO, 5-30% by weight of B ₂ O ₃ , 6- 15% by weight SiO ₂ , 0.5-5% by weight Al ₂ O ₃ , and 3-10% by weight BaO.

In addition, the present invention relates to a laminated ceramic component comprising a plurality of dielectric layers; internal electrodes formed between the dielectric layers; and external electrodes electrically connected to the internal electrodes, wherein the dielectric layer is formed by sintering a dielectric ceramic composition The resultant dielectric ceramic is formed, and the internal electrodes are formed of elemental Cu or elemental Ag or an alloy material containing Cu or Ag as a main component.

(2) The second embodiment of the present invention

In order to solve the above-mentioned problems, the present inventors have also made in-depth research and obtained the following results. That is, if a glass containing at least ZnO and B ₂ O ₃ is added to a mixture containing ZnTiO ₃ , Zn ₂ TiO ₄ and Al ₂ O ₃ and, if necessary, TiO ₂ , ε _r within the preferred range can be obtained And smaller dielectric loss tanδ (high Q value), and even after sintering at 800-1000 ° C, it will not change the formation between ZnTiO ₃ , Zn ₂ TiO ₄ , TiO ₂ and Al ₂ O ₃ . With glass containing ZnO, dissolution of ZnO components from ZnTiO ₃ and Zn ₂ TiO ₄ into the glass can be suppressed as much as possible, so that changes in dielectric properties caused by composition changes can be suppressed. Thus, using Cu, Ag, etc. as a wiring conductor enables lamination and fine pattern wiring.

The present invention relates to a dielectric ceramic composition, which comprises 100 parts by weight of a main component represented by the general formula xZn ₂ TiO ₄ -yZnTiO ₃ -zTiO ₂ -wAl ₂ O ₃ , wherein x satisfies 0.15<x<1.0 and y satisfies 0<y<0.85, z satisfies 0≤z≤0.2, w satisfies 0<w≤0.2, and satisfies x+y+z+w=1; and contains 3-30 parts by weight of lead-free low-melting point glass, said no Leaded _low -melting _point glass containing 50-75% by weight of ZnO, 5-30% by weight of _B2O3 , 6-15% by weight of _SiO2 , 0.5-5% by weight of _Al2O3 , and 3-10% by weight The BaO. In a preferred embodiment of the dielectric ceramic composition of the present invention, x satisfies 0.15<x<0.99, y satisfies 0.05<y<0.85, and w satisfies 0.005<w≦0.2.

The present invention also relates to a dielectric ceramic containing Zn ₂ TiO ₄ , ZnTiO ₃ , TiO ₂ and Al ₂ O ₃ crystalline phases (wherein the TiO ₂ phase can be omitted) and a glass phase, said dielectric ceramic being obtained by sintering a dielectric ceramic composition .

In addition, the present invention relates to a method for producing a dielectric ceramic composition, which includes the steps _{of :} mixing ZnO raw _material powder and TiO ₂ raw _material powder, and _calcining them to obtain A ceramic powder whose content may be 0); the resulting ceramic powder is mixed with _Al2O3 and lead-free low-melting glass containing 50-75% _by weight of ZnO, 5-30% by weight of _B2 O ₃ , 6-15% by weight SiO ₂ , 0.5-5% by weight Al ₂ O ₃ , and 3-10% by weight BaO.

In addition, the present invention relates to a laminated ceramic component comprising a plurality of dielectric layers; internal electrodes formed between the dielectric layers; and external electrodes electrically connected to the internal electrodes, wherein the dielectric layer is formed by sintering a dielectric ceramic composition The resultant dielectric ceramic is formed, and the internal electrodes are formed of elemental Cu or elemental Ag or an alloy material containing Cu or Ag as a main component.

The dielectric ceramic composition of the present invention contains a crystalline component containing Zn ₂ TiO ₄ , ZnTiO ₃ , and TiO ₂ as optional components, and a specific glass component. Thus, sintering may be performed at a temperature of 1000°C or below. The dielectric ceramic obtained by sintering the dielectric ceramic composition can have a relative permittivity ε _r of about 15-25, a small dielectric loss, and an absolute value of the temperature coefficient of the resonance frequency of 50 ppm/°C or less . As a result, a laminated ceramic part with internal electrodes made of elemental Cu, elemental Ag, or an alloy material containing Cu or Ag as a main component can be obtained.

Another dielectric ceramic composition of the present invention comprises a crystalline component containing Zn ₂ TiO ₄ , ZnTiO ₃ , Al ₂ O ₃ and TiO ₂ as optional components and a specific glass component. Thus, sintering may be performed at a temperature of 1000°C or below. The dielectric ceramic obtained by sintering the dielectric ceramic composition can have a relative permittivity ε _r of about 10-40, preferably about 15-25, its dielectric loss can be small, and the absolute value of the temperature coefficient of its resonance frequency It may be 50 ppm/°C or less. In addition, a dielectric ceramic composition can be obtained in which the above-mentioned characteristics are less changed by the influence of sintering temperature. As a result, a laminated ceramic part with internal electrodes made of elemental Cu, elemental Ag, or an alloy material containing Cu or Ag as a main component can be obtained.

Brief description of the drawings

FIG. 1 is a schematic perspective view of a tri-plate resonator according to an embodiment of the present invention;

Fig. 2 is a schematic cross-sectional view of the resonator in Fig. 1;

Fig. 3 shows the X-ray diffraction pattern of the pellets obtained by sintering the dielectric ceramic composition of Example 1 of the present invention;

Figure 4 shows the X-ray diffraction pattern of the pellets obtained by sintering the dielectric ceramic composition of Example 15 of the present invention;

The reference number 1 refers to the dielectric layer, 2 refers to the inner electrode, and 3 refers to the outer electrode.

The best mode of implementation of the present invention

(1) The first embodiment of the present invention

The dielectric ceramic composition of the first embodiment of the present invention will be specifically described as follows.

The composition of the present invention is a dielectric ceramic composition containing a main component containing Zn ₂ TiO ₄ , ZnTiO ₃ , and TiO ₂ as optional components, and a glass component. The main component is represented by the general formula x'Zn ₂ TiO ₄ -(1-x'-y')ZnTiO ₃ -y'TiO ₂ , where x' is in the range of 0.15<x'<0.8 and y' is in the range of 0≤y'≤ 0.2 range. The glass composition is lead-free low-melting glass, which contains 50-75% by weight of ZnO, 5-30% by weight of B ₂ O ₃ , 6-15% by weight of SiO ₂ , and 0.5-5% by weight of Al ₂ O ₃ , and 3-10% by weight of BaO. The dielectric ceramic composition of the present invention contains 3-30 parts by weight of the glass component per 100 parts by weight of the main component.

In the above composition, x' should preferably be greater than 0.15 and less than 0.8. For the case where x' is 0.15 or less or 0.8 or more, the absolute value of τ _f exceeds 50 ppm/°C, which is not desirable.

In addition, in the above composition, y' should preferably be in the range of 0-0.2. The specific permittivity tends to slightly increase due to the inclusion of TiO ₂ . However, for compositions where y' is equal to less than 0.2, the object effect of the present invention can be obtained. If y' is greater than 0.2, τ _f exceeds +50 ppm/°C, which is not desirable.

In the dielectric ceramic composition of the present invention, the amount of the glass component should preferably be in the range of 3 to 30 parts by weight per 100 parts by weight of the main components constituting the ceramic substrate. In the case where the amount of the glass component is less than 3 parts by weight, the sintering temperature is equal to or higher than the melting point of Ag or Cu or an alloy containing Ag or Cu as a main component. Electrodes made of such materials are therefore not ideal for use. If the amount of the glass component exceeds 30 parts by weight, good sintering tends to be difficult due to elution of glass.

Zn ₂ TiO ₄ used in the present invention can be produced by mixing zinc oxide ZnO and titanium oxide TiO ₂ at a molar ratio of 2:1 and calcining the resulting mixture. ZnTiO ₃ can be prepared by mixing zinc oxide ZnO and titanium oxide TiO ₂ at a molar ratio of 1:1 and calcining the resulting mixture. In addition to TiO ₂ and ZnO, nitrates, carbonates, hydroxides, chlorides, and organometallic compounds containing Zn and/or Ti can be used as raw materials for Zn ₂ TiO ₄ and ZnTiO ₃ for calcination oxides are formed.

The dielectric ceramic composition is characterized by containing a predetermined amount of a specific glass. The glass used in the present invention contains 50-75% by weight of ZnO, 5-30% by weight of B ₂ O ₃ , 6-15% by weight of SiO ₂ , 0.5-5% by weight of Al ₂ O ₃ , and 3-10% by weight % BaO. These oxide components are mixed in a predetermined ratio and melted, cooled and vitrified.

The composition of the glass used in the present invention will be described below. For ZnO, if the ratio is less than 50% by weight, the softening point of the glass is too high to perform good sintering, and if the ratio is higher than 75% by weight, vitrification at a desired temperature becomes difficult. For _B2O3 , if the ratio is less than 5% by weight, the softening point of _the glass is too high to perform good sintering, and if the ratio is higher than 30% by weight, good sintering cannot be performed due to dissolution of the glass. sintering. For SiO ₂ , if the ratio is lower than 6% by weight or higher than 15% by weight, the softening point of the glass is too high to perform good sintering. For Al ₂ O ₃ , if the ratio is less than 0.5% by weight, the chemical durability of the resulting dielectric ceramic will deteriorate, and if the ratio exceeds 5% by weight, it will be difficult to vitrify at a desired temperature. When the ratio of BaO is less than 3% by weight or more than 10% by weight, it is difficult to perform vitrification at a desired temperature. If the glass contains Pb or Bi components, the Q value of the dielectric ceramic composition tends to decrease. Since the glass in the dielectric ceramic composition of the present invention does not contain Pb, it will not cause environmental pollution caused by Pb.

According to the present invention, for 100 parts by weight of the main component represented by the general formula x'Zn ₂ TiO ₄ -(1-x'-y')ZnTiO ₃ -y'TiO ₂ , wherein x' is in the range of 0.15<x'<0.8 And y' is in the range of 0≤y'≤0.2, containing 3-30 parts by weight of lead-free low-melting point glass, the lead-free low-melting point glass contains 50-75% by weight of _ZnO , 5-30% by weight of _B2O3 , 6-15% by weight of SiO ₂ , 0.5-5% by weight of Al ₂ O ₃ , and 3-10% by weight of BaO. Therefore, sintering can be achieved at lower temperatures of 800-1000°C. The dielectric ceramic of the present invention can be obtained by sintering the above dielectric ceramic composition. The dielectric ceramic of the present invention is characterized by a relative permittivity ε _r of about 15-25, a high no-load Q value, and an absolute value of a temperature coefficient τ _f of a resonator frequency of 50 ppm/°C or less. The composition of the dielectric ceramic is basically the same as the raw material composition of the dielectric ceramic composition, and both contain crystal phases and glass phases of Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ . According to the dielectric ceramic composition of the present invention, low-temperature sintering can be performed to obtain a dielectric ceramic having the above-mentioned characteristics.

In the present invention, Zn ₂ TiO ₄ , ZnTiO ₃ particles, TiO ₂ particles and glass particles as optional components are individually pulverized and mixed before sintering. Alternatively, the respective raw material particles are mixed with each other and pulverized before sintering. In order to obtain improved dispersibility, high no-load Q value and stable relative permittivity ε _r , the average particle diameter of the above raw materials before sintering should preferably be equal to or lower than 2.0 μm, more preferably equal to or lower than 1.0 μm. If the average particle size is too small, it may be difficult to handle in some cases. Thus, the average particle diameter should also preferably be equal to or higher than 0.05 μm.

Next, the dielectric ceramic composition and the method for producing the dielectric ceramic of the present invention will be described. ZnO raw material powder and TiO ₂ raw material powder were mixed and calcined, thereby obtaining a ceramic powder containing Zn ₂ TiO ₄ and ZnTiO ₃ and TiO ₂ as an optional ingredient. The ceramic powder is mixed with lead-free low-melting glass containing 50-75% by weight of ZnO, 5-30% by weight of B ₂ O ₃ , 6-15% by weight of SiO ₂ , 0.5-5% by weight % of Al ₂ O ₃ , and 3-10% by weight of BaO. Thus, a dielectric ceramic composition was obtained. Each of the ceramic powders Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ can be prepared separately. Alternatively, the ratio between ZnO and TiO ₂ raw materials may be adjusted to directly obtain a powder containing Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ in a mixed state.

A separate preparation method of each powder of Zn ₂ TiO ₄ and ZnTiO ₃ for obtaining the dielectric ceramic composition of the present invention will be further described below. First, zinc oxide and titanium dioxide in a molar ratio of 2:1 are weighed and mixed together with a solvent such as water, alcohol, or the like. Subsequently, water, alcohol, etc. are removed from the resultant, and then calcined at a temperature of 900-1200° C. for 1-5 hours in an oxygen-containing atmosphere (for example, in an air atmosphere). The calcined powder thus obtained consisted of Zn ₂ TiO ₄ . Then, weigh titanium dioxide and zinc oxide at a molar ratio of 1:1. ZnTiO ₃ was prepared in the same preparation method as Zn ₂ TiO ₄ . A predetermined amount of main components containing Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ is weighed. Further, the lead-free low _- melting glass containing 50-75 wt% of ZnO, 5-30 wt% of _B2O3 , 6-15 wt% of SiO ₂ , 0.5-5% by weight Al ₂ O ₃ , and 3-10% by weight BaO. Mix the glass and main ingredients together with a solvent such as water, alcohol, etc. Water, alcohol, and the like are subsequently removed, followed by pulverization, thereby producing an intended dielectric ceramic composition, which is a raw material powder for dielectric ceramics.

Dielectric ceramic pellets were formed by sintering the dielectric ceramic composition of the present invention, and their dielectric properties were measured. More specifically, an organic binder such as polyvinyl alcohol is mixed with the raw material powder for dielectric ceramics so as to be homogenized. Drying and pulverization are carried out, and the resultant is then compressed into pellets (under a pressure of 100-1000 Kg/cm ² ). The resulting formation is sintered at 800-1000° C. in an oxygen-containing gas atmosphere such as air, thereby obtaining a dielectric ceramic in which Zn ₂ TiO ₄ phase, ZnTiO ₃ phase and TiO ₂ phase coexist with a glass phase.

As required, the dielectric ceramic composition of the present invention according to the first embodiment is processed into a suitable shape and size, or formed into a sheet using the dielectric ceramic composition based on a doctor blade method or the like, and lamination of the sheet and electrodes is performed. Thus, the dielectric ceramic composition can be used as a material constituting various types of laminated ceramic parts. The laminated ceramic component may be a laminated ceramic capacitor, LC filter, dielectric resonator, dielectric substrate, and the like.

A laminated ceramic part according to a first embodiment of the present invention has a plurality of dielectric layers, internal electrodes formed between the dielectric layers, and external electrodes electrically connected to the internal electrodes. The dielectric layer is composed of a dielectric ceramic obtained by sintering the dielectric ceramic composition according to the first embodiment of the present invention. The internal electrodes are made of elemental Cu or elemental Ag, or an alloy material containing Cu or Ag as a main component. The laminated ceramic part of the present invention can be produced by simultaneously sintering a dielectric layer composed of a dielectric ceramic and elemental Cu, elemental Ag, or an alloy material containing Cu or Ag as a main component.

An embodiment of the laminated ceramic component of the present invention according to the first embodiment may be a three-layer plate type resonator as shown in FIGS. 1 and 2 . FIG. 1 is a schematic perspective view of a three-layer plate resonator according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view of FIG. 1 . As shown in Figures 1 and 2, the three-layer plate resonator is a laminated ceramic component with a plurality of dielectric layers 1, internal electrodes 2 formed between the dielectric layers, and electrically connected to the internal electrodes The external electrode 3. The three-layer plate resonator is manufactured by laminating a plurality of dielectric layers 1 and an internal electrode 2 placed in the center. The internal electrode 2 is formed in such a way as to penetrate from the first surface A of the resonator to the second surface B opposite to the first surface A. As shown in FIG. Only the first side A is open. The external electrodes 3 are formed on the five faces except the first face A on the resonator. The internal electrode 2 and the external electrode 3 are connected to each other on the second side B. As shown in FIG. The material of the internal electrodes 2 contains Cu or Ag, or an alloy material containing Cu or Ag as a main component. Since the dielectric ceramic composition of the present invention can be sintered at a low temperature, the above-mentioned materials for internal electrodes can be used.

(2) The second embodiment of the present invention

Hereinafter, a dielectric ceramic composition according to a second embodiment of the present invention will be described in detail.

The composition of the present invention is a dielectric ceramic composition comprising a main component containing Zn ₂ TiO ₄ , ZnTiO ₃ and Al ₂ O ₃ and TiO ₂ as an optional component, and a glass component. The main component is represented by the general formula xZn ₂ TiO ₄ -yZnTiO ₃ -zTiO ₂ -wAl ₂ O ₃ , where x is in the range of 0.15<x<1.0, y is in the range of 0<y<0.85, z is in the range of 0≤z≤0.2, w is in the range of 0<w≤0.2 and satisfies x+y+z+w=1. Each of Zn ₂ TiO ₄ , ZnTiO ₃ , Al ₂ O ₃ and TiO ₂ has a crystal form. In another aspect, the glass composition may be a glass containing 50-75% by weight of ZnO and 5-30% by weight _{of B2O3} . In the dielectric ceramic composition of the present invention, every 100 parts by weight of the main component corresponds to 3-30 parts by weight of the glass component.

In the above composition, the mole fraction x of Zn ₂ TiO ₄ is preferably in the range of greater than 0.15 and less than 1.0, especially greater than 0.15 and less than 0.99. If x is equal to or less than 0.15 or x is 1.0, the absolute value of τ _f exceeds 50 ppm/°C, which is not desirable.

Also in the above composition, the mole fraction y of ZnTiO ₃ is preferably in the range greater than 0 and less than 0.85, especially greater than 0.005 and less than 0.85. If y is 0 or y is equal to or greater than 0.85, the absolute value of τ _f exceeds 50 ppm/°C, which is not desirable.

Also in the above composition, the mole fraction z of _TiO2 is preferably in the range of 0-0.2. The dielectric constant tends to increase slightly due to the inclusion of TiO ₂ . However, any composition in which z is equal to or less than 0.2 can achieve the objective advantages of the present invention. If z is larger than 0.2, the absolute value of τ _f exceeds +50 ppm/°C, which is not desirable.

Also in the above composition, the mole fraction w of Al ₂ O ₃ is preferably greater than 0 and not greater than 0.2, particularly greater than 0.005 and not greater than 0.2. If w is 0, the change in dielectric properties caused by the change in sintering temperature becomes large, thereby narrowing the sintering temperature range, which is not ideal. If w is greater than 0.2, the sintering temperature will be equal to or higher than the melting point of Ag or Cu or an alloy containing Ag or Cu as a main component. This prevents the use of electrodes made of the above-mentioned materials which are the object of the present invention and is therefore not desirable.

Also in the dielectric ceramic composition of the present invention, the glass component is preferably used in an amount ranging from 3 to 30 parts by weight per 100 parts by weight of main components constituting the ceramic substrate. If the amount of the glass component is less than 3 parts by weight, the sintering temperature will be equal to or higher than the melting point of Ag or Cu or an alloy containing Ag or Cu as a main component. Therefore, electrodes made of the above-mentioned materials cannot be used, which is not desirable. If the amount of the glass component used exceeds 30% by weight, good sintering tends to be difficult due to elution of the glass.

Zn ₂ TiO ₄ used in the present invention can be prepared by mixing zinc oxide ZnO and titanium dioxide TiO ₂ at a molar ratio of 2:1 and calcining the resulting mixture. ZnTiO ₃ can be prepared by mixing zinc oxide ZnO and titanium dioxide TiO ₂ at a molar ratio of 1:1 and calcining the resulting mixture. In addition to TiO ₂ and ZnO, nitrates, carbonates, hydroxides, chlorides, and organometallic compounds containing Zn and/or Ti can be used as raw materials for Zn ₂ TiO ₄ and ZnTiO ₃ for calcination oxides are formed.

The glass used in the present invention is preferably a glass containing 50-75% by weight of ZnO. Since the ZnO component is contained in the glass, the transfer of the ZnO components of Zn ₂ TiO ₄ and ZnTiO ₃ constituting the main components to the glass phase can be suppressed. Changes in dielectric properties caused by compositional changes during sintering can thus be reduced. In addition, if the glass contains 5-30% by weight of _B2O3 , ideally low temperature sintering can be easily _performed . A particularly preferred glass composition contains 50-75% by weight ZnO, 5-30% by weight B ₂ O ₃ , 6-15% by weight SiO ₂ , 0.5-5% by weight Al ₂ O ₃ , and 3-10% by weight % BaO. In the case of a dielectric ceramic composition in which the glass component is mixed with the above main component, the relative permittivity ε _r may preferably be in the range of 15-25. The preparation method used as the glass to be mixed is to melt, cool and vitrify the above-mentioned respective oxide components mixed in a predetermined ratio. The composition of the glass used in the present invention will be described below. For ZnO, if the ratio is less than 50% by weight, the softening point of the glass is too high to perform good sintering, and if the ratio is higher than 75% by weight, vitrification at a desired temperature becomes difficult. For _B2O3 , if the ratio is less than 5% by weight, the softening point of _the glass is too high to perform good sintering, and if the ratio is higher than 30% by weight, good sintering cannot be performed due to dissolution of the glass. sintering. For SiO ₂ , if the ratio is lower than 6% by weight or higher than 15% by weight, the softening point of the glass is too high to perform good sintering. For Al ₂ O ₃ , if the ratio is less than 0.5% by weight, the chemical durability of the resulting dielectric ceramic will deteriorate, and if the ratio exceeds 5% by weight, it will be difficult to vitrify at a desired temperature. When the ratio of BaO is less than 3% by weight or more than 10% by weight, it is difficult to perform vitrification at a desired temperature. If the glass contains Pb or Bi components, the Q value of the dielectric ceramic composition tends to decrease. Since the glass in the dielectric ceramic composition of the present invention does not contain Pb, it will not cause environmental pollution caused by Pb.

According to the present invention, for every 100 parts by weight of the main component represented by the general formula xZn ₂ TiO ₄ -yZnTiO ₃ -zTiO ₂ -wAl ₂ O ₃ , wherein x satisfies 0.15<x<1.0, y satisfies 0<y<0.85, z It satisfies 0≤z≤0.2, w satisfies 0<w≤0.2, and satisfies x+y+z+w=1, and contains 3-30 parts by weight of glass components containing ZnO and B ₂ O ₃ . Therefore, sintering can be accomplished at lower temperatures of 800-1000°C. The dielectric ceramic of the present invention can be obtained by sintering the above dielectric ceramic composition. The dielectric ceramic of the present invention is characterized by a relative permittivity _εr of 10-40, preferably about 15-25, a high no-load Q value, and an absolute value of the temperature coefficient _τf of its resonant frequency of 50ppm/°C or more Low. The composition of the dielectric ceramic is basically the same as the raw material composition of the dielectric ceramic composition, and both contain crystal phases and glass phases of Zn ₂ TiO ₄ , ZnTiO ₃ , TiO ₂ and Al ₂ O ₃ . According to the dielectric ceramic composition of the present invention, low-temperature sintering can be performed to obtain a dielectric ceramic having the above-mentioned characteristics.

The dielectric ceramic composition of the present invention takes the form of a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ , TiO ₂ , Al ₂ O ₃ and glass before sintering. Even if the mixture is further mixed with additives added such as solvents, organic materials, etc. during the preparation process, the resultant mixed product is the dielectric ceramic composition contemplated by the present invention. Even after the mixture of the ceramic composition of the present invention is sintered, the composition of the crystalline phase and the glass phase is less changed. Accordingly, the dielectric ceramic obtained by sintering the mixture is a dielectric ceramic composed of the dielectric ceramic composition of the present invention.

In the present invention, Zn ₂ TiO ₄ , ZnTiO ₃ , TiO ₂ and Al ₂ O ₃ particles and glass particles are individually pulverized and mixed before sintering. Alternatively, the raw material particles are mixed with each other and pulverized before sintering. In order to obtain improved dispersibility, high no-load Q value and stable relative permittivity ε _r , the average particle diameter of the above raw materials before sintering should preferably be equal to or lower than 2.0 μm, more preferably equal to or lower than 1.0 μm. If the average particle size is too small, it may be difficult to handle in some cases. Thus, the average particle diameter should also preferably be equal to or higher than 0.05 μm.

Next, the dielectric ceramic composition and the method for producing the dielectric ceramic of the present invention will be described. Each of the Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ powders constituting a part of the main component can be prepared individually. Alternatively, by adjusting the ratio between ZnO and TiO ₂ raw materials, calcination can be performed to directly obtain the mixed powder of Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ . In order to obtain mixed powders of Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ in one calcining step, raw material powders of ZnO and TiO ₂ may be mixed in a preset ratio and calcined. The resulting substance can be mixed with a predetermined amount of _Al2O3 , and then can be used as the main component of the dielectric ceramic composition of the present invention _. In order to obtain the dielectric ceramic composition of the present invention, 100 parts by weight of the main component may be mixed with 3-30 parts by weight of a glass component containing 50-75% by weight of ZnO and 5-30% by weight of _B2 O ₃ .

In a preferred production method of the dielectric ceramic composition, ZnO raw material powder and TiO ₂ raw material powder are mixed and calcined to obtain a ceramic powder containing Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ . The ceramic powder is mixed with a predetermined amount of lead-free low-melting glass containing 50-75% by weight of ZnO, 5-30% by weight of B ₂ O ₃ , 6-15% by weight of SiO ₂ , 0.5- 5% by weight of Al ₂ O ₃ , and 3-10% by weight of BaO.

If the respective ceramic powders of Zn ₂ TiO ₄ and ZnTiO ₃ are prepared individually, titanium dioxide (TiO ₂ ) and zinc oxide (ZnO) can be mixed in a molar ratio of 2:1 and 1:1 to prepare Zn ₂ TiO ₄ and ZnTiO ₃ , followed by calcination. Predetermined amounts of the obtained Zn ₂ TiO ₄ , ZnTiO ₃ , TiO ₂ and Al ₂ O ₃ are weighed and mixed, and then the resulting mixture can be used as the main component of the dielectric ceramic composition of the present invention.

The individual preparation methods of Zn ₂ TiO ₄ , ZnTiO ₃ powders for preparing the dielectric ceramic composition of the present invention will be described in detail below. First, titanium dioxide (TiO ₂ ) and zinc oxide (ZnO) in a molar ratio of 2:1 are weighed and mixed together with a solvent such as water, alcohol, or the like. Subsequently, water, alcohol, etc. are removed from the resulting substance. The resulting material is then pulverized and calcined at 900-1200° C. for 1-5 hours in an oxygen-containing atmosphere (eg, air atmosphere). The calcined powder thus obtained consisted of Zn ₂ TiO ₄ . Then, weigh titanium dioxide and zinc oxide at a molar ratio of 1:1. ZnTiO ₃ was prepared in the same preparation method as Zn ₂ TiO ₄ . Zn ₂ TiO ₄ , ZnTiO ₃ and further TiO ₂ , Al ₂ O ₃ , and glass are weighed in predetermined proportions, and mixed together with a solvent such as water, alcohol, or the like. Water, alcohol, etc. are subsequently removed, and the resultant is then pulverized to obtain the intended dielectric ceramic composition, which is a raw material powder for dielectric ceramics.

Dielectric ceramic pellets were formed by sintering the dielectric ceramic composition of the present invention, and their dielectric properties were measured. More specifically, an organic binder such as polyvinyl alcohol is mixed with the raw material powder for dielectric ceramics so as to be homogenized. Drying and pulverization are carried out, and the resultant is then compressed into pellets (under a pressure of 100-1000 Kg/cm ² ). The resulting formation is sintered at 800-1000° C. in an oxygen-containing gas atmosphere such as air to obtain a dielectric ceramic in which Zn ₂ TiO ₄ phase, ZnTiO ₃ phase, TiO ₂ phase and Al ₂ O ₃ phase coexist with a glass phase.

The dielectric ceramic composition according to the second embodiment can be used as various laminated ceramic parts, as in the first embodiment.

The laminated ceramic part of the present invention according to the second embodiment is obtained in the same manner as the first embodiment, except that the dielectric ceramic for the dielectric layer is obtained by sintering the dielectric ceramic composition of the present invention according to the second embodiment. get.

Example

Examples of the present invention and related comparative examples will be described below.

[Example 1]

(Example belonging to the first embodiment of the present invention)

0.33 moles of titanium dioxide (TiO ₂ ) and 0.66 moles of zinc oxide (ZnO) were placed in a ball mill together with ethanol and mixed for 12 hours. The solvent was removed from the solution, and the resultant was pulverized and calcined at 1000° C. in an air atmosphere, thereby obtaining Zn ₂ TiO ₄ calcined powder. Then, 0.5 mol of TiO ₂ and 0.5 mol of ZnO were mixed and calcined in the same manner as above to obtain ZnTiO ₃ calcined powder. The Zn ₂ TiO ₄ and ZnTiO ₃ calcined powders thus obtained were mixed with TiO ₂ at the ratios shown in Table 1 to prepare a base material (main component). Add 10 parts by weight of glass powder to 100 parts by weight of the above substrate, the composition of the glass powder is 63.5 wt% of ZnO, 8 wt% of SiO ₂ , 1.5 wt% of Al ₂ O ₃ , 7 wt% of BaO, and 20% by weight of _B2O3 , the resulting mass was placed in a ball mill and mixed for 24 _hours . The solvent was removed from the solution, and the resulting substance was pulverized until the average particle diameter was 1 μm. An appropriate amount of polyvinyl alcohol solution was added to the obtained pulverized product, followed by drying. Subsequently, the resulting substance was shaped into a pellet having a diameter of 12 mm and a thickness of 4 mm, and the resulting pellet was sintered at 900° C. for 2 hours in an air atmosphere. Figure 3 shows the X-ray diffraction pattern of the obtained sintered pellets. It can be seen from Fig. 3 that Zn ₂ TiO ₄ phase, ZnTiO ₃ phase and TiO ₂ phase co-exist in the sintered pellets of the dielectric ceramic composition of the present invention.

The dielectric ceramic thus obtained was processed into a size of 7 mm in diameter and 3 mm in thickness. Then the no-load Q value at the resonant frequency 7-11GHz, the relative permittivity ε _r and the temperature coefficient τ _f of the resonant frequency were measured according to the dielectric resonance method. Table 2 shows the results.

[Table 1] Substrate composition (mole fraction) Glass Composition (wt%) Substrate dosage (parts by weight) Amount of glass (parts by weight) Average particle size after pulverization (μm) Zn ₂ TiO ₄ x' ZnTiO ₃ 1-x'-y' TiO ₂ y' SiO ₂ Al ₂ O ₃ ZnO BaO B ₂ O ₃ Bi ₂ O ₃ PbO Example 1 0.22 0.77 0.01 8.0 1.5 63.5 7.0 20.0 0.0 0.0 100 10 1 2 0.40 0.59 0.01 8.0 1.5 63.5 7.0 20.0 0.0 0.0 100 10 1 3 0.75 0.24 0.01 8.0 15 63.5 7.0 20.0 0.0 0.0 100 10 1 4 0.22 0.78 0.00 8.0 1.5 63.5 7.0 20.0 0.0 0.0 100 10 1 5 0.20 0.70 0.10 8.0 1.5 63.5 7.0 20.0 0.0 0.0 100 10 1 6 0.18 0.62 0.20 8.0 1.5 63.5 7.0 20.0 0.0 0.0 100 10 1 7 0.22 0.77 0.01 8.0 1.5 63.5 7.0 20.0 0.0 0.0 100 10 2 8 0.22 0.77 0.01 8.0 1.5 63.5 7.0 20.0 0.0 0.0 100 10 0.5 9 0.22 0.77 0.01 8.0 1.5 63.5 7.0 20.0 0.0 0.0 100 10 0.1 10 0.22 0.77 0.01 6.0 1.5 71.0 3.5 18.0 0.0 0.0 100 10 1 11 0.22 0.77 0.01 8.0 5.0 50.0 10.0 27.0 0.0 0.0 100 10 1 12 0.22 0.77 0.01 10.0 5.0 50.0 5.0 30.0 0.0 0.0 100 10 1 13 0.22 0.77 0.01 8.0 1.5 63.5 7.0 20.0 0.0 0.0 100 5 1 14 0.22 0.77 0.01 8.0 1.5 63.5 7.0 20.0 0.0 0.0 100 25 1 comparative example 1 0.10 0.86 0.01 8.0 1.5 63.5 7.0 20.0 0.0 0.0 100 10 1 2 0.85 0.14 0.01 8.0 1.5 63.5 7.0 20.0 0.0 0.0 100 10 1 3 0.16 0.54 0.30 8.0 1.5 63.5 7.0 20.0 0.0 0.0 100 10 1 4 0.11 0.39 0.50 8.0 1.5 63.5 7.0 20.0 0.0 0.0 100 10 1 5 0.22 0.77 0.01 8.0 1.5 18.5 7.0 20.0 45.0 0.0 100 10 1 6 0.22 0.77 0.01 8.0 1.5 20.5 7.0 20.0 0.0 43.0 100 10 1 7 0.22 0.77 0.01 20.0 0.5 75.0 2.5 2.0 0.0 0.0 100 10 1 8 0.22 0.77 0.01 17.0 7.0 42.0 1.0 33.0 0.0 0.0 100 10 1 9 0.22 0.77 0.01 10.0 5.0 33.0 2.0 50.0 0.0 0.0 100 10 1 10 0.22 0.77 0.01 4.0 1.6 66.3 7.3 20.9 0.0 0.0 100 10 1 11 0.22 0.77 0.01 18.0 1.3 56.6 6.2 17.8 0.0 0.0 100 10 1 12 0.22 0.77 0.01 8.1 0.1 64.4 7.1 20.3 0.0 0.0 100 10 1 13 0.22 0.77 0.01 7.6 7.0 60.0 6.6 18.9 0.0 0.0 100 10 1 14 0.22 0.77 0.01 11.4 2.1 48.0 10.0 28.5 0.0 0.0 100 10 1 15 0.22 0.77 0.01 4.4 0.8 80.0 3.8 11.0 0.0 0.0 100 10 1 16 0.22 0.77 0.01 8.4 1.6 66.9 2.0 21.1 0.0 0.0 100 10 1 17 0.22 0.77 0.01 7.6 1.4 60.1 12.0 18.9 0.0 0.0 100 10 1 18 0.22 0.77 0.01 9.6 1.8 76.2 8.4 4.0 0.0 0.0 100 10 1 19 0.22 0.77 0.01 6.5 1.2 51.6 5.7 35.0 0.0 0.0 100 10 1 20 0.22 0.77 0.01 8.0 1.5 63.5 7.0 20.0 0.0 0.0 100 2 1 twenty one 0.22 0.77 0.01 8.0 1.5 63.5 7.0 20.0 0.0 0.0 100 40 1

[Table 2] _εr Q×f(GHz) τ _f (ppm/℃) Sintering temperature/℃ Example 1 20.0 10000 0 900 2 19.3 10000 -5 900 3 18.0 9000 -43 900 4 19.8 10000 -3 900 5 22.1 12000 15 900 6 24.5 13000 30 900 7 20.0 10000 0 900 8 19.0 8000 10 900 9 17.5 6000 30 900 10 19.5 13000 -20 900 11 18.0 12000 -5 900 12 16.0 8000 -20 900 13 22.0 13000 10 900 14 18.0 7500 -10 900 comparative example 1 23.5 12000 55 900 2 17.2 7000 -55 900 3 26.0 13000 53 900 4 42.0 14000 80 900 5 24.0 1000 -60 900 6 25.0 2000 -70 900 7 Unsintered at a temperature equal to or lower than 1000°C 8 Glass dissolves at a temperature equal to or higher than 800°C 9 Glass dissolves at a temperature equal to or higher than 800°C 10 Unsintered at a temperature equal to or lower than 1000°C 11 Unsintered at a temperature equal to or lower than 1000°C 12 Melt in 4% by weight sulfuric acid solution 13 Unsintered at a temperature equal to or lower than 1000°C 14 Unsintered at a temperature equal to or lower than 1000°C 15 Unsintered at a temperature equal to or lower than 1000°C 16 Unsintered at a temperature equal to or lower than 1000°C 17 Unsintered at a temperature equal to or lower than 1000°C 18 Unsintered at a temperature equal to or lower than 1000°C 19 Glass dissolves at a temperature equal to or higher than 800°C 20 Unsintered at a temperature equal to or lower than 1000°C twenty one Glass dissolves at a temperature equal to or higher than 900°C

According to the doctor blade method, to a 100 g mixture of substrate and glass, 9 g of polyvinyl butyral as binder, 6 g of dibutyl phthalate as plasticizer and 60 g of toluene and 30 g of isopropyl alcohol to prepare a green sheet with a thickness of 100 μm. Then, 22 layers of the green sheets were laminated by a thermocompression bonding method applying a pressure of 200 kg/cm ² at 65°C. At this time, the layer printed with Ag as the internal electrode was disposed so as to be provided at the center in the thickness direction. External electrodes were formed after sintering the resulting laminate at 900° C. for 2 hours, thereby producing a three-layer plate-type resonator. The dimensions of the resonator are 4.9mm wide, 1.7mm high, and 8.4mm long.

The no-load Q value of the resulting three-layer plate resonator was evaluated at a resonance frequency of 2 GHz. As a result, the no-load Q value of the three-layer plate resonator was 210. Thus, by using the dielectric ceramic composition of the present invention, a three-layer plate type resonator having excellent characteristics can be obtained.

[Examples 2 and 3]

(belonging to the example of the first embodiment):

(effect of x')

In the same manner as in Example 1 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ mixed in the ratio shown in Table 1 was used as a base material. The substrates were likewise mixed with glass in the proportions indicated in Table 1. Then, sintered pellets were produced under the same conditions as in Example 1, and the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Example 4-6]

(belonging to the example of the first embodiment):

(effect of y')

In the same manner as in Example 1 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ mixed in the ratio shown in Table 1 was used as a base material. The substrates were likewise mixed with glass in the proportions indicated in Table 1. Then, sintered pellets were produced under the same conditions as in Example 1, and the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Example 7-9]

(belonging to the example of the first embodiment):

(Effect of particle size)

In the same manner as in Example 1 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ mixed in the ratio shown in Table 1 was used as a base material. The base material was also mixed with glass in the ratio shown in Table 1, and the resultant was pulverized until its particle size reached the average particle size shown in Table 1. Then, sintered pellets were produced under the same conditions as in Example 1, and the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Example 10-12]

(belonging to the example of the first embodiment):

(Effect of glass composition)

In the same manner as in Example 1 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ mixed in the ratio shown in Table 1 was used as a base material. The substrates were likewise mixed in the proportions indicated in Table 1 with the glasses of the respective compositions. Then, sintered pellets were produced under the same conditions as in Example 1, and the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Example 13-14]

(belonging to the example of the first embodiment)

(Effect of glass amount)

In the same manner as in Example 1 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ mixed in the ratio shown in Table 1 was used as a base material. The substrates were likewise mixed with glass in the proportions indicated in Table 1. Then, sintered pellets were produced under the same conditions as in Example 1, and the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Examples 1 and 2]

(effect of x')

In the same manner as in Example 1 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ mixed in the ratio shown in Table 1 was used as a base material. The substrates were likewise mixed with glass in the proportions indicated in Table 1. Then, sintered pellets were produced under the same conditions as in Example 1. However, when the molar ratio x' of Zn ₂ TiO ₄ is less than 0.15, the temperature coefficient τ _f of the resonance frequency exceeds +50 ppm/°C. When x' is greater than 0.8, the temperature coefficient τ _f of the resonance frequency is less than -50ppm/°C. The results are shown in Table 2.

[Comparative Examples 3 and 4]

(effect of y')

In the same manner as in Example 1 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ mixed in the ratio shown in Table 1 was used as a base material. The substrates were likewise mixed with glass in the proportions indicated in Table 1. Then, sintered pellets were produced under the same conditions as in Example 1. However, when the molar ratio y' of _TiO2 is greater than 0.2, the temperature coefficient _τf of the resonance frequency exceeds +50ppm/°C. The results are shown in Table 2.

[Comparative Examples 5-19]

(Effect of glass composition)

In the same manner as in Example 1 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ mixed in the ratio shown in Table 1 was used as a base material. The substrates were likewise mixed in the proportions indicated in Table 1 with the glasses of the respective composition. Then, sintered pellets were produced under the same conditions as in Example 1. Yet, when adopting the composition of the glass beyond the range adopted by the present invention, the Q value decreases, the temperature coefficient τ _f of the resonance frequency is lower than -50ppm/°C (Comparative Examples 5 and 6), and the glass is melted by sulfuric acid solution (Comparative Example 12), or the pellets could not be sintered at a temperature equal to or lower than 1000°C, or the glass was eluted at a temperature equal to or higher than 800°C (Comparative Examples 7-11 or 13-19). The results are shown in Table 2.

[Comparative Examples 20 and 21]

(Effect of glass amount)

In the same manner as in Example 1 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ and TiO ₂ mixed in the ratio shown in Table 1 was used as a base material. The substrates were likewise mixed with glass in the proportions indicated in Table 1. Then, sintered pellets were produced under the same conditions as in Example 1. However, when the amount of glass used is less than 3 parts by weight, sintering cannot be achieved at a temperature equal to or lower than 1000°C. When the amount of glass used is higher than 30 parts by weight, the glass dissolves and reacts with a setter at a temperature equal to or higher than 900°C. The results are shown in Table 2.

[Example 15]

(belonging to the example of the second embodiment of the present invention)

0.33 moles of titanium dioxide (TiO ₂ ) and 0.66 moles of zinc oxide (ZnO) were placed in a ball mill together with ethanol and mixed for 12 hours. The solvent was removed from the solution, and the resultant was pulverized and calcined at 1000° C. in an air atmosphere, thereby obtaining Zn ₂ TiO ₄ calcined powder. Then, 0.5 mol of TiO ₂ and 0.5 mol of ZnO were mixed and calcined in the same manner as above to obtain ZnTiO ₃ calcined powder. The Zn ₂ TiO ₄ and ZnTiO ₃ calcined powders thus obtained were mixed with TiO ₂ and Al ₂ O ₃ in the ratios shown in Table 3 to prepare substrates (main components). Add 10 parts by weight of glass powder to 100 parts by weight of the above substrate, the composition of the glass powder is 63.5 wt% of ZnO, 8 wt% of SiO ₂ , 1.5 wt% of Al ₂ O ₃ , 7 wt% of BaO, and 20% by weight of _B2O3 , the resulting mass was placed in a ball mill and mixed for 24 _hours . The solvent was removed from the solution, and the resulting substance was pulverized until the average particle diameter was 1 μm. An appropriate amount of polyvinyl alcohol solution was added to the obtained pulverized product, followed by drying. Subsequently, the resulting mass was shaped into pellets with a diameter of 12 mm and a thickness of 4 mm, and the resulting pellets were sintered at 850° C. for 2 hours in an air atmosphere (Example 15a). Figure 4 shows the X-ray diffraction pattern of the obtained sintered pellets. It can be seen from Fig. 4 that Zn ₂ TiO ₄ phase, ZnTiO ₃ phase, TiO ₂ phase and Al ₂ O ₃ phase co-exist in the sintered pellets of the dielectric ceramic composition of the present invention. Another pellet obtained in the same way was sintered in the same way at 950°C for 2 hours (Example 15b).

The dielectric ceramic thus obtained was processed into a size of 7 mm in diameter and 3 mm in thickness. Then the no-load Q value at the resonant frequency 7-11GHz, the relative permittivity ε _r and the temperature coefficient τ _f of the resonant frequency were measured according to the dielectric resonance method. Table 4 shows the results.

[table 3] Substrate composition (mole fraction) Glass Composition (wt%) Substrate dosage (parts by weight) Amount of glass (parts by weight) Average particle size after pulverization (μm) Zn ₂ TiO ₄ x ZnTiO ₃ y TiO ₂ z Al ₂ O ₃ w SiO ₂ Al ₂ O ₃ ZnO BaO B ₂ O ₃ Example 15a,b 0.22 0.76 0.01 0.01 8.0 l.5 63.5 7.0 20.0 100 10 1 16a,b 0.40 0.58 0.01 0.01 8.0 1.5 63.5 7.0 20.0 100 10 1 17a,b 0.80 0.18 0.01 001 8.0 1.5 63.5 7.0 20.0 100 10 1 18a,b 0.97 0.01 0.01 0.01 8.0 1.5 63.5 7.0 20.0 100 10 1 19a,b 0.22 0.77 0.00 0.01 8.0 1.5 63.5 7.0 20.0 100 10 1 20a,b 0.20 0.69 0.10 0.01 8.0 1.5 63.5 7.0 20.0 100 10 1 21a,b 0.18 0.61 0.20 0.01 8.0 1.5 63.5 7.0 20.0 100 10 1 22a,b 0.22 0.75 0.01 0.02 8.0 1.5 63.5 7.0 20.0 100 10 1 23a,b 0.21 0.73 0.01 0.05 8.0 1.5 63.5 7.0 20.0 100 10 1 24a,b 0.19 0.65 0.01 0.15 8.0 1.5 63.5 7.0 20.0 100 10 1 25a,b 0.22 0.76 0.01 0.01 7.0 3.0 75.0 10.0 5.0 100 10 1 26a,b 0.22 0.76 0.01 0.01 6.0 1.5 72.0 2.5 18.0 100 10 1 27a,b 0.22 0.76 0.01 0.01 8.0 5.0 50.0 10.0 27.0 100 10 1 28a,b 0.22 0.76 0.01 0.01 10.0 5.0 50.0 5.0 30.0 100 10 1 29a,b 0.22 0.76 0.01 0.01 8.0 1.5 63.5 7.0 20.0 100 5 1 30a,b 0.22 0.76 0.01 0.01 8.0 1.5 63.5 7.0 20.0 l00 25 1 comparative example 22a,b 0.10 0.88 0.01 0.01 8.0 1.5 63.5 7.0 20.0 l00 10 1 23a,b 0.98 0.00 0.01 0.01 8.0 1.5 63.5 7.0 20.0 100 10 1 24a,b 0.15 0.54 0.30 0.01 8.0 1.5 63.5 7.0 20.0 100 10 1 25a,b 0.11 0.38 0.50 0.01 8.0 1.5 63.5 7.0 20.0 100 10 1 26a,b,c 0.22 0.77 0.01 0 8.0 1.5 63.5 7.0 20.0 100 10 1 27 0.16 0.58 0.01 0.25 8.0 1.5 63.5 7.0 20.0 100 10 1 28 0.22 0.76 0.01 0.01 20.0 0.5 75.0 2.5 2.0 100 10 1 29 0.22 0.76 0.01 0.01 17.0 7.0 42.0 1.0 33.0 100 10 1 30 0.22 0.76 0.01 0.01 10.0 5.0 33.0 2.0 50.0 100 10 1 31 0.22 0.76 0.01 0.01 25.0 1.5 45.0 8.5 20.0 100 10 1 32 0.22 0.76 0.01 0.01 6.0 1.5 80.0 7.5 5.0 100 10 1 33 0.22 0.76 0.01 0.01 4.0 1.6 66.3 7.3 20.9 100 10 1 34 0.22 0.76 0.01 0.01 18.0 1.3 56.6 6.2 17.8 100 10 1 35 0.22 0.76 0.01 0.01 8.1 0.1 64.4 7.1 20.3 100 10 1 36 0.22 0.76 0.01 0.01 7.6 7.0 60.0 6.6 18.9 100 10 1 37 0.22 0.76 0.01 0.01 11.4 2.1 48.0 10.0 28.5 100 10 1 38 0.22 0.76 0.01 0.01 4.4 0.8 80.0 3.8 11.0 100 10 1 39 0.22 0.76 0.01 0.01 8.4 1.6 66.9 2.0 21.1 100 10 1 40 0.22 0.76 0.01 0.01 7.6 1.4 60.1 12.0 18.9 100 10 1 41 0.22 0.76 0.01 0.01 9.6 1.8 76.2 8.4 4.0 100 10 1 42 0.22 0.76 0.01 0.01 6.5 1.2 51.6 5.7 35.0 100 10 1 43 0.22 0.76 0.01 0.01 6.0 1.5 80.0 7.5 5.0 100 2 1 44 0.22 0.76 0.01 0.01 6.0 1.5 80.0 7.5 5.0 100 40 1

[Table 4] _εr Q×f(GHz) τ _f (ppm/℃) Sintering temperature/℃ Example 15a 20.0 10000 0 850 15b 20.0 10000 0 950 16a 19.3 10000 -5 850 16b 19.3 10000 -5 950 17a 17.7 9000 -30 850 17b 17.7 9000 -30 950 18a 17.0 9000 -50 850 18b 17.0 9000 -50 950 19a 20.0 10000 -1 850 19b 20.0 10000 -1 950 20a 22.1 12000 15 850 20b 22.1 12000 15 950 21a 24.5 13000 30 850 21b 24.5 13000 30 950 22a 20.0 10000 0 850 22b 20.0 10000 0 950 23a 19.0 8000 10 850 23b 19.0 8000 10 950 24a 17.5 6000 30 850 24b 17.5 6000 30 950 25a 18.5 13000 -15 850 25b 18.5 13000 -15 950 26a 19.5 13000 -20 850 26b 19.5 13000 -20 950 27a 18.0 12000 -5 850 27b 18.0 12000 -5 950 28a 16.0 8000 -20 850 28b 16.0 8000 -20 950 29a 22.0 13000 10 850 29b 22.0 13000 10 950 30a 18.0 7500 -10 850 30b 18.0 7500 -10 950 comparative example 22a 23.5 12000 55 850 22b 23.5 12000 55 950 23a 16.5 6000 -60 850 23b 16.5 6000 -60 950 24a 26.0 13000 53 850 24b 26.0 13000 53 950 25a 42.0 14000 80 850 25b 42.0 14000 80 950 26a 20.0 10000 -54 850 26b 20.0 10000 0 900 26c 20.0 10000 20 950 27 Unsintered at a temperature equal to or lower than 1000°C 28 Unsintered at a temperature equal to or lower than 1000°C 29 Glass dissolves at a temperature equal to or lower than 800°C 30 Glass dissolves at a temperature equal to or lower than 800°C 31 Unsintered at a temperature equal to or lower than 1000°C 32 Unsintered at a temperature equal to or lower than 1000°C 33 Unsintered at a temperature equal to or lower than 1000°C 34 Unsintered at a temperature equal to or lower than 1000°C 35 Melt in 4% by weight sulfuric acid solution 36 Unsintered at a temperature equal to or lower than 1000°C 37 Unsintered at a temperature equal to or lower than 1000°C 38 Unsintered at a temperature equal to or lower than 1000°C 39 Unsintered at a temperature equal to or lower than 1000°C 40 Unsintered at a temperature equal to or lower than 1000°C 41 Unsintered at a temperature equal to or lower than 1000°C 42 Glass dissolves at a temperature equal to or lower than 800°C 43 Unsintered at a temperature equal to or lower than 1000°C 44 Glass dissolves at a temperature equal to or lower than 800°C

According to the doctor blade method, to a 100 g mixture of substrate and glass, 9 g of polyvinyl butyral as binder, 6 g of dibutyl phthalate as plasticizer and 60 g of toluene and 30 g of isopropyl alcohol to prepare a green sheet having a thickness of 100 μm. Then, 22 layers of the green sheets were laminated by a thermocompression bonding method applying a pressure of 200 kg/cm ² at 65°C. At this time, the layer printed with Ag as the internal electrode was disposed so as to be provided at the center in the thickness direction. External electrodes were formed after sintering the resulting laminate at 900° C. for 2 hours, thereby producing a three-layer plate-type resonator. The dimensions of the resonator are 4.9mm wide, 1.7mm high, and 8.4mm long.

The no-load Q value of the resulting three-layer plate resonator was evaluated at a resonance frequency of 2 GHz. As a result, the no-load Q value of the three-layer plate resonator was 210. Thus, by using the dielectric ceramic composition of the present invention, a three-layer plate type resonator having excellent characteristics can be obtained.

[Example 16-18]

(belonging to the example of the second embodiment)

(effect of x and y)

In the same manner as in Example 15 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ , TiO ₂ and Al ₂ O ₃ mixed in the ratios shown in Table 3 was used as a substrate. The substrates were also mixed with glass in the proportions indicated in Table 3. Then, sintered pellets were produced under the same conditions as in Example 15, and the characteristics were evaluated in the same manner as in Example 15. The results are shown in Table 4.

[Example 19-21]

(belonging to the example of the second embodiment):

(effect of z)

In the same manner as in Example 15 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ , TiO ₂ and Al ₂ O ₃ mixed in the ratios shown in Table 3 was used as a substrate. The substrates were also mixed with glass in the proportions indicated in Table 3. Then, sintered pellets were produced under the same conditions as in Example 15, and the characteristics were evaluated in the same manner as in Example 15. The results are shown in Table 4.

[Example 22-24]

(belonging to the example of the second embodiment):

(effect of w)

In the same manner as in Example 15 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ , TiO ₂ and Al ₂ O ₃ mixed in the ratios shown in Table 3 was used as a substrate. The substrates were also mixed with glass in the proportions indicated in Table 3. Then, sintered pellets were produced under the same conditions as in Example 15, and the characteristics were evaluated in the same manner as in Example 15. The results are shown in Table 4. It can be seen that the dielectric ceramic composition of the present invention containing _Al2O3 in these examples provides the following stable characteristics: suitable relative _permittivity , small dielectric loss (high Q value), and at 850-950 The difference in the temperature coefficient τ _f of the resonant frequency is small when sintering is carried out at a wide range of sintering temperatures of ℃.

[Example 25-28]

(belonging to the example of the second embodiment):

(Effect of glass composition)

In the same manner as in Example 15 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ , TiO ₂ and Al ₂ O ₃ mixed in the ratios shown in Table 3 was used as a substrate. The base material was also mixed with the glass of each composition in the ratio shown in Table 3, and the resulting mass was pulverized until its particle size reached the average particle size shown in Table 3. Then, sintered pellets were produced under the same conditions as in Example 15, and the characteristics were evaluated in the same manner as in Example 15. The results are shown in Table 4.

[Examples 29 and 30]

(belonging to the example of the second embodiment):

(Effect of glass amount)

In the same manner as in Example 15 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ , TiO ₂ and Al ₂ O ₃ mixed in the ratios shown in Table 3 was used as a substrate. The substrates were also mixed with glass in the proportions indicated in Table 3. Then, sintered pellets were produced under the same conditions as in Example 15, and the characteristics were evaluated in the same manner as in Example 15. The results are shown in Table 4.

[Comparative Examples 22 and 23]

(effect of x and y)

In the same manner as in Example 15 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ , TiO ₂ and Al ₂ O ₃ mixed in the ratios shown in Table 3 was used as a substrate. The substrates were also mixed with glass in the proportions indicated in Table 3. Then, sintered pellets were produced under the same conditions as in Example 15. However, when the molar ratio x of Zn ₂ TiO ₄ is equal to or less than 0.15 or the molar ratio y of ZnTiO ₃ is equal to or greater than 0.85, the temperature coefficient τ _f of the resonance frequency is greater than +50 ppm/°C. When y is equal to 0, the temperature coefficient τ _f of the resonance frequency is less than -50ppm/°C. The results are shown in Table 4.

[Comparative Examples 24 and 25]

(effect of z)

In the same manner as in Example 15 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ , TiO ₂ and Al ₂ O ₃ mixed in the ratios shown in Table 3 was used as a substrate. The substrates were also mixed with glass in the proportions indicated in Table 3. Then, sintered pellets were produced under the same conditions as in Example 15. However, when the molar ratio z of _TiO2 is greater than 0.2, then the temperature coefficient _τf of the resonance frequency is greater than +50ppm/°C. The results are shown in Table 4.

[Comparative Examples 26 and 27]

(effect of w)

In the same manner as in Example 15 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ , TiO ₂ and Al ₂ O ₃ mixed in the ratios shown in Table 3 was used as a substrate. The substrates were also mixed with glass in the proportions indicated in Table 3. Then, sintered pellets were produced under the same conditions as in Example 15 (sintering at 900° C. was additionally performed). However, when the molar ratio w of Al ₂ O ₃ is equal to 0, then in the case of sintering temperature of 850°C, the temperature coefficient τ _f of the resonance frequency is greater than 50ppm/°C, and the temperature coefficient τ _f of the resonance frequency is between 850- The sintering temperature range of 950°C is unstable and changes greatly. When w is equal to or higher than 0.2, the sintering temperature is equal to or higher than 1000°C. The results are shown in Table 4.

[Comparative Examples 28-42]

(Effect of glass composition)

In the same manner as in Example 15 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ , TiO ₂ and Al ₂ O ₃ mixed in the ratios shown in Table 3 was used as a substrate. The substrates were likewise mixed in the proportions indicated in Table 3 with the glasses of the respective compositions. Then, sintered pellets were produced under the same conditions as in Example 15. However, when a glass composition out of the range adopted in the present invention is used, it occurs that the glass is melted by a sulfuric acid solution (Comparative Example 35), or the pellet cannot be sintered at a temperature equal to or lower than 1000° C., or the glass is sintered at a temperature equal to or lower than Dissolution at temperatures above 800°C (Comparative Examples 28-34 or 36-42). The results are shown in Table 4.

[Comparative Examples 43 and 44]

(Effect of glass amount)

In the same manner as in Example 15 above, a mixture of Zn ₂ TiO ₄ , ZnTiO ₃ , TiO ₂ and Al ₂ O ₃ mixed in the ratios shown in Table 3 was used as a substrate. The substrates were also mixed with glass in the proportions indicated in Table 3. Then, sintered pellets were produced under the same conditions as in Example 15. However, when the amount of glass used is less than 3 parts by weight, sintering cannot be achieved at a temperature equal to or lower than 1000°C. When the amount of glass used is greater than 30 parts by weight, the glass will dissolve at 900° C. and react with the curing agent. The results are shown in Table 4.

Industrial applicability

The dielectric ceramic composition of the present invention can be sintered at a temperature equal to or lower than the melting point of Ag or Cu or the melting point of an alloy containing Ag or Cu as a main component, which is difficult to achieve in conventional techniques. Therefore, according to the dielectric ceramic composition of the present invention, such metals can be used as internal conductor materials in the packaging and multilayering of electronic components in the manufacture of electronic components. The dielectric ceramic obtained by sintering the dielectric ceramic composition of the present invention has a relative permittivity of about 10-40, preferably about 15-25, and has a small dielectric loss tanδ (high Q value), and 50ppm/°C or The absolute value of the temperature coefficient τ _f for lower dielectric frequencies. According to the present invention, there are provided a dielectric ceramic composition and a manufacturing method for obtaining said dielectric ceramic, in particular a dielectric ceramic composition and a dielectric ceramic composition with small characteristic changes and differences caused by changes in sintering temperature and small compositional changes during sintering. Manufacturing method. Furthermore, according to the present invention, there is provided a laminated ceramic part, such as a laminated ceramic capacitor or an LC filter, with a dielectric layer made of the above dielectric ceramic composition and an internal electrode containing Ag or Cu or an alloy containing Ag or Cu as a main component.

Claims (8)

1. dielectric ceramic composition, it comprises:

100 weight part general formulas are x ' Zn ₂TiO ₄-(1-x '-y ') ZnTiO ₃-y ' TiO ₂Principal constituent, wherein x ' satisfies 0.15＜x '＜0.8, y ' satisfies 0≤y '≤0.2; With

3-30 weight part Unlead low-smelting point glass, described Unlead low-smelting point glass contains the ZnO of 50-75 weight %, the B of 5-30 weight % ₂O ₃, the SiO of 6-15 weight % ₂, the Al of 0.5-5 weight % ₂O ₃And the BaO of 3-10 weight %.

2. media ceramic, it comprises Zn ₂TiO ₄, ZnTiO ₃And TiO ₂Crystallization phases (TiO wherein ₂Can save mutually) and glassy phase, described media ceramic obtains by the dielectric ceramic composition of sintering claim 1.

3. make the method for the dielectric ceramic composition of claim 1, it comprises following steps:

With ZnO raw material powder and TiO ₂Raw material powder mixes and calcining, obtains containing Zn ₂TiO ₄, ZnTiO ₃And TiO ₂Ceramic powder (TiO wherein ₂Content can be 0); With

Described ceramic powder is mixed with Unlead low-smelting point glass, and described Unlead low-smelting point glass contains the ZnO of 50-75 weight %, the B of 5-30 weight % ₂O ₃, the SiO of 6-15 weight % ₂, the Al of 0.5-5 weight % ₂O ₃And the BaO of 3-10 weight %.

4. laminated ceramic parts, it comprises:

A plurality of medium layers;

Be formed at the interior electrode between the medium layer; With

The outer electrode that is electrically connected with interior electrode,

Wherein medium layer is made of the media ceramic that the dielectric ceramic composition by sintering claim 1 obtains, and interior electrode is by element Cu or elements A g or contain Cu or Ag forms as the alloy material of principal constituent.

5. dielectric ceramic composition, it comprises:

100 weight part general formulas are xZn ₂TiO ₄-yZnTiO ₃-zTiO ₂-wAl ₂O ₃Principal constituent, wherein x satisfies 0.15＜x＜1.0, y satisfies 0＜y＜0.85, z satisfies 0≤z≤0.2, w satisfies 0＜w≤0.2, and satisfies x+y+z+w=1; With

3-30 weight part Unlead low-smelting point glass, described Unlead low-smelting point glass contains the ZnO of 50-75 weight %, the B of 5-30 weight % ₂O ₃, the SiO of 6-15 weight % ₂, the Al of 0.5-5 weight % ₂O ₃And the BaO of 3-10 weight %.

6. media ceramic, it comprises Zn ₂TiO ₄, ZnTiO ₃, TiO ₂And Al ₂O ₃Crystallization phases (TiO wherein ₂Can save mutually) and glassy phase, described media ceramic obtains by the dielectric ceramic composition of sintering claim 5.

7. make the method for the dielectric ceramic composition of claim 5, it comprises following steps:

With ZnO raw material powder and TiO ₂Raw material powder mixes and calcining, obtains containing Zn ₂TiO ₄, ZnTiO ₃And TiO ₂Ceramic powder (TiO wherein ₂Content can be 0); With

With described ceramic powder and Al ₂O ₃Mix with Unlead low-smelting point glass, described Unlead low-smelting point glass contains the ZnO of 50-75 weight %, the B of 5-30 weight % ₂O ₃, the SiO of 6-15 weight % ₂, the Al of 0.5-5 weight % ₂O ₃And the BaO of 3-10 weight %.

8. laminated ceramic parts, it comprises:

A plurality of medium layers;

Be formed at the interior electrode between the medium layer; With

The outer electrode that is electrically connected with interior electrode,

Wherein medium layer is made of the media ceramic that the dielectric ceramic composition by sintering claim 5 obtains, and interior electrode is by element Cu or elements A g or contain Cu or Ag forms as the alloy material of principal constituent.

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