JPH07201645A - Ceramic capacitor and its production - Google Patents

Abstract

PURPOSE:To provide a ceramic capacitor, and production method, in which a dielectric ceramic composition having good AC voltage characteristics of dielectric loss is employed a dielectric layer while sustaining the conventional electric characteristics. CONSTITUTION:A dielectric ceramic composition is produced by firing a mixture of 100.0wt.% of basic component and 0.2-5.0wt.% of additive components. The basic component comprises a substance represented by a formula; {(Ba1-v-w-xCavSrwMgx)O}k(Ti1-y-zZryRz)O2-z/2+alphaM1+betaM2 (where, R represents one or more than one kind of element selected from La-Eu, R' represents one or more than one kind of element selected from Sc-Lu, M1 represents P and/or V, and M2 represents one or more than one kind of element selected from Cr, Mn, Fe, Ni and Co). The additive components comprises Li2O or B2O3 SiO2 and MO (where, MO represents one or more than one kind of oxide selected from BaO, SrO, CaO, MgO and ZnO).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic capacitor having a single-layer or laminated structure in which one or more dielectric ceramic layers are sandwiched by at least two internal electrodes, and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, a laminated porcelain capacitor is formed by printing an unsintered porcelain sheet (green sheet) made of dielectric porcelain raw material powder with a conductive paste containing a noble metal such as platinum or palladium as a main component in a desired pattern. It is manufactured by stacking a plurality of unsintered porcelain sheets, press-bonding them, and firing them at a temperature of 1300 ° C to 1600 ° C in an oxidizing atmosphere.

Here, the conductive paste containing a noble metal such as platinum or palladium as a main component is used. If the conductive paste containing a noble metal as a main component is used, a laminated ceramic capacitor is used. This is because the conductive paste will not be oxidized even if it is baked at a high temperature of 1300 ° C. to 1600 ° C. in an oxidizing atmosphere, and a desired internal electrode can be obtained. However, since noble metals such as platinum and palladium are expensive materials, the conventional laminated porcelain capacitor has a problem of high cost.

Therefore, in order to reduce the manufacturing cost of the laminated ceramic capacitor, it is desired to develop a laminated ceramic capacitor using a base metal such as nickel as the material of the internal electrodes. However, when a base metal such as nickel is used as a material for the internal electrodes, it is 1300 ° C to 1600 ° C in the atmosphere.
The internal electrode cannot be formed because the material of the internal electrode is oxidized by the firing at ℃ and the oxide easily reacts with the material of the dielectric layer.

As a method of preventing the oxidation of the material of the internal electrodes, firing in a reducing atmosphere can be considered. However, firing in a reducing atmosphere causes the material of the dielectric layer to be significantly reduced, resulting There was a problem that the resulting product would not function as a capacitor.

Therefore, the applicant of the present invention has proposed various dielectric porcelain compositions capable of obtaining desired electric characteristics even by firing at a temperature of 1300 ° C. to 1600 ° C. in a reducing atmosphere. And, these dielectric ceramic compositions are disclosed in the following patent publications.

That is, Japanese Patent Publication No. 60-20851 discloses a basic component consisting of {(Ba _x Ca _y Sr _z ) O} _k (Ti _n Zr _1-n ) O ₂ , Li ₂ O and SiO ₂ . MO (however, MO is BaO,
Disclosed is a dielectric ceramic composition containing an additive component composed of one or more oxides selected from CaO and SrO.

In Japanese Patent Laid-Open No. 61-147404, a basic component consisting of {(Ba _1-xy Ca _x Sr _y ) O} _k (Ti _1-z Zr _z ) O ₂ and B ₂ O ₃ A dielectric porcelain composition is disclosed which contains, and an additive component composed of SiO ₂ and MO.

Further, in Japanese Patent Application Laid-Open No. 61-147405, a basic component composed of {(Ba _1-xy Ca _x Sr _y ) O} _k (Ti _1-z Zr _z ) O ₂ and B ₂ O ₃ There is disclosed a dielectric ceramic composition containing SiO and an additive component composed of SiO ₂ .

In Japanese Patent Laid-Open No. 147406/1986, a basic component consisting of {(Ba _1-xy Ca _x Sr _y ) O} _K (Ti _1-z Zr _z ) O ₂ and B ₂ O ₃ are disclosed. And SiO ₂ and MO (where MO is Ba
Disclosed is a dielectric ceramic composition containing an additive component consisting of one or more oxides selected from O, CaO and SrO.

The dielectric ceramic composition disclosed in each of these publications can be obtained by firing at a relatively low temperature of 1200 ° C. or lower in a reducing atmosphere,
Its relative permittivity ε is 5000 or more, and its resistivity ρ is 1 × 10 ⁶
It is MΩ · cm or more.

[0012]

By the way, with the recent pursuit of miniaturization and high density of electronic circuits, there is a strong demand for miniaturization and large capacity of porcelain capacitors. Attempts have been made to solve this by thinning the film and increasing the number of layers.

However, in the laminated ceramic capacitor, thinning the dielectric ceramic layer increases the AC voltage per unit thickness, which results in a dielectric loss (tan).
There is a problem that δ) becomes large.

The present invention maintains the electrical characteristics of the dielectric ceramic composition disclosed in the above-mentioned respective publications, and further uses a dielectric ceramic composition having a good AC voltage characteristic of dielectric loss as a dielectric layer. An object of the present invention is to provide a capacitor and a manufacturing method thereof.

[0015]

In order to solve the above-mentioned problems, the first and second aspects of the present invention provide one or more dielectric porcelain layers made of a dielectric porcelain composition and the dielectric porcelain layer. In a porcelain capacitor having at least two or more internal electrodes sandwiched between the dielectric porcelain composition,
It consists of a mixture of 00.0 parts by weight of the basic component and 0.2 to 5.0 parts by weight of the additive component, and the basic component is ((Ba _1-vwx Ca _v Sr _w Mg _x ). O} _k (Ti _1-yz Zr _y R _z ) O
_{2-z / 2} + αM ₁ + βM ₂ (where R is Sc, Y, Gd, D
one or more elements selected from y, Ho, Er, Yb, Tb, Tm and Lu, M ₁ is P and / or V,
M ₂ is 1 selected from Cr, Mn, Fe, Ni, Co
Or two or more elements, v, w, x, y, z, k, α and β are 0.00 ≦ v ≦ 0.27 0.00 ≦ w ≦ 0.37 0.00 ≦ x ≦ 0 0.03 0.00 <y <0.26 0.05 ≦ 0.6 w + y ≦ 0.26 0.002 ≦ z ≦ 0.04 1.00 ≦ k ≦ 1.04 0.0005 ≦ α ≦ 0.01 0 0.0005 ≦ β ≦ 0.01).

Here, Ca in the composition formula of the basic component
Of the number of atoms, that is, the value of v is 0.00 ≦ v ≦ 0.
The reason for setting 27 is that if the value of v is within this range,
A dielectric ceramic composition having desired electrical characteristics, flat temperature characteristics, and high resistivity ρ can be obtained, but when 0.27 is exceeded, a dense sintered body is obtained. This is because the firing temperature of 1 is too high, exceeding 1250 ° C., and the relative dielectric constant ε _s is also less than 7,000.

Since Ca is an element used for flattening the temperature characteristics of the porcelain capacitor and improving the resistivity ρ as described above, it is not necessary to contain Ca, that is, the value of v. It is possible to obtain a dielectric porcelain composition having desired electrical characteristics even when the value of is zero.

The ratio of the number of Mg atoms in the composition formula of the basic component, that is, the value of x is 0.00 ≦ x ≦ 0.0.
The reason for setting 3 is that when the value of x is within this range, a dielectric ceramic composition having desired electrical characteristics can be obtained, but when the value of x exceeds 0.03, This is because the relative permittivity ε _{s of the} dielectric porcelain composition sharply decreases and becomes worse than less than 7,000.

Since Mg has a function of shifting the Curie point to the low temperature side, a function of flattening the temperature characteristics and a function of improving the resistivity ρ, like Mg, even if it is not intentionally contained, That is, even if the value of x is zero, a dielectric ceramic composition having desired electrical characteristics can be obtained.

The value of the relational expression 0.6w + y is 0.05.
≦ 0.6w + y ≦ 0.26 is the relational expression 0.6w
When the value of + y is within this range, a dielectric ceramic composition having desired electrical characteristics can be obtained, but the value of the relational expression 0.6w + y is less than 0.05, or 0.2
When the value exceeds 6, the relative permittivity ε _s is 70 in both cases.
This is because it becomes worse when it is less than 00.

Here, the range of the value of the relational expression 0.6w + y is defined by Sr and Zr in which the ratio is shown by w and y.
This is because all are elements that shift the Curie point to the low temperature side, and it is necessary to consider them as a whole. However,
The characteristic of Sr as a shifter is 3 when Zr is 1.
Since it is / 5 (= 0.6), w is corrected by multiplying the coefficient by 0.6.

The value of the relational expression 0.6w + y is 0.26.
Even if it is below, when the value of w exceeds 0.37, the relative permittivity ε _s becomes poor at less than 7,000. Therefore, the relational expression 0.
The upper limit of 6w + y is 0.26, but at the same time, the upper limit of w must be 0.37. Therefore, S
The ratios of r and Zr are 0 ≦ w ≦ 0.37 and 0 <y ≦ 0.
Within the range of 26, and 0.05 ≦ 0.6w + y
The range must satisfy ≦ 0.26.

Further, the ratio of the number of R atoms in the composition formula of the basic component, that is, the value of z is 0.002 ≦ z ≦ 0.0.
The reason for setting 4 is that when the value of z is within this range, a dielectric porcelain composition having desired electrical characteristics can be obtained, but when it is less than 0.002, the dielectric ceramic composition is obtained. The loss tan δ is significantly deteriorated, and the resistivity ρ is also 1 × 10 ⁴ MΩ ・
If it is less than cm and exceeds 0.04, 1250
This is because a dense sintered body cannot be obtained even by firing at ℃.

The R components Sc, Y, Gd, Dy, H
o, Er, Yb, Tb, Tm and Lu work almost in the same way, and the same result can be obtained by using one or a plurality of them selected from them. Further, among the R components in the composition formula of the basic component, although Lu is not shown in Table 3, this also has the same action and effect as other R components.

In addition, in the composition formula of the basic component, {(Ba
_1-vwx Ca _v Sr _w Mg _x ) O}, that is, the value of k is 1.0
0 ≦ k ≦ 1.04 means that when the value of k is within this range, a dielectric ceramic composition having desired electrical characteristics can be obtained, but it is less than 1.00. When the resistivity ρ is less than 1 × 10 ⁶ MΩ · cm, the resistivity is significantly deteriorated. When it exceeds 1.04, a dense sintered body cannot be obtained even by firing at 1250 ° C. Is.

Further, the ratio of M ₁ in the composition formula of the basic component, that is, the value of α is set to 0.0005 ≦ α ≦ 0.01, because when the value of α is within this range, It is possible to obtain a dielectric porcelain composition having the electrical characteristics of, but when the value of α is less than 0.0005, the AC voltage is 20
This is because the dielectric loss tan δ at 0 V / mm exceeds 5.0% and deteriorates, and when the value of α exceeds 0.01, the resistivity ρ deteriorates to 1.0 × 10 ⁴ MΩ · cm or less. .

Incidentally, P and V of the M ₁ component work almost in the same manner, and P within the range where 0.0005 ≦ α ≦ 0.01 is satisfied.
One or both of V and V can be used.

The ratio of M ₂ in the composition formula of the basic component, that is, the value of β is set to 0.0005 ≦ β ≦ 0.01, if the value of β is within this range, It is possible to obtain a dielectric porcelain composition having the electrical characteristics of, but if the value of β is less than 0.0005, the AC voltage is 20
The dielectric loss tan δ at 0 V / mm exceeds 5.0% and deteriorates. When the value of β exceeds 0.01, the relative dielectric constant is 7
This is because it becomes worse at less than 000.

The M ₂ components Cr, Mn, Fe, C
o and Ni work almost in the same way, and similar results can be obtained by using one selected from these or by using a combination of a plurality of them.

Further, a small amount of a mineralizing agent may be added to the basic components within a range not impairing the object of the present invention to improve the sinterability. Moreover, you may add another substance as needed. Further, as a starting material for obtaining the basic components, oxides other than those shown in the examples may be used, or hydroxides or other compounds may be used.

The addition amount of the additive component is 0.2 to 5.0 parts by weight with respect to 100 parts by weight of the basic component.
When the added amount of the additive component is within this range, 1190 to
A dielectric ceramic composition having desired electrical characteristics can be obtained by firing at 1200 ° C., but if it is less than 0.2 parts by weight, a dense sintered body can be obtained even if the firing temperature is 1250 ° C. If the amount exceeds 5.0 parts by weight, the relative permittivity ε _s becomes less than 7,000.

In the invention according to claim 1, the additive components are Li ₂ O, SiO ₂ and MO (where MO is Ba.
O, SrO, CaO, MgO, and one or more oxides selected from ZnO), said Li ₂ O
And a composition range of the SiO ₂ and the MO, in a triangular diagram showing these compositions in mol%, the composition in which the Li ₂ O is 1 mol%, the SiO ₂ is 80 mol%, and the MO is 19 mol%. And a first point A indicating 1 mol% of the Li ₂ O, 39 mol% of the SiO _{2 and} 60 mol% of the MO.
The second point B indicating the composition of the above, 30 mol% of Li ₂ O, 30 mol% of SiO ₂ , and 40 mol% of MO.
The third point C indicating the composition, the Li ₂ O content of 50 mol%, the SiO ₂ content of 50 mol%, the MO content of 0 mol%, and the Li ₂ O content. 20 mol%,
It is in a region surrounded by five straight lines connecting the fifth point E indicating the composition of 80 mol% of SiO _{2 and} 0 mol% of MO in this order.

Here, the composition of the additive component is changed to Li ₂ O--S.
In the triangular diagram showing the composition ratio of iO ₂ -MO in mol%,
The region surrounded by the five straight lines connecting the points A to E in this order is defined as a dielectric porcelain composition having desired electrical characteristics if the composition of the additive component is within this range. However, if the composition of the additive component is out of this range, a dense sintered body cannot be obtained even by firing at 1250 ° C. In addition, BaO, which becomes the MO component,
SrO, CaO, MgO and ZnO may be used in suitable ratios.

According to the second aspect of the invention, the additive components are B ₂ O ₃ , SiO ₂ and MO (where MO is BaO,
SrO, CaO, MgO and ZnO selected from the group consisting of one or more kinds of oxides), and the composition range of the B ₂ O ₃ , the SiO ₂ and the MO is such that these compositions are expressed in mol%. In the triangular diagram shown, the B ₂ O ₃ content is 1 mol%, the SiO ₂ content is 80 mol%, and the MO content is 19 mol%.
A sixth point F indicating the composition of B ₂ O ₃ is 1 mol%,
A seventh point G showing a composition of 39 mol% of SiO _{2 and} 60 mol% of MO, 30 mol% of B ₂ O _3, 0 mol% of SiO _{2 and} 70 mol% of MO. An eighth point H indicating the composition, 90 mol% of B ₂ O _{3 and} S of
A ninth point I showing a composition of 0 mol% of iO _{2 and} 10 mol% of MO, 90 mol% of B ₂ O _{3 and} SiO 2
_A tenth point J showing a composition in which ₂ is 10 mol% and the MO is 0 mol%, and a composition in which the B ₂ O ₃ is 20 mol%, the SiO ₂ is 80 mol% and the MO is 0 mol%. It is within the area surrounded by six straight lines connecting the eleventh point K shown in this order.

Here, the composition of the additive component is changed to B ₂ O ₃ --S.
In the triangular diagram showing the composition ratio of iO ₂ -MO in mol%,
The region surrounded by the six straight lines connecting the points F to K in this order is defined as a dielectric porcelain composition having desired electrical characteristics if the composition of the additive component is within this range. However, if the composition of the additive component is out of this range, a dense sintered body cannot be obtained even by firing at 1250 ° C. In addition, BaO, which becomes the MO component,
SrO, CaO, MgO and ZnO may be used in suitable ratios.

Further, the inventions according to claims 3 and 4 for solving the above-mentioned problems, include a step of preparing a mixture of unsintered porcelain powder comprising the basic component and the additive component, and the step of preparing the mixture. Forming a non-sintered porcelain sheet, forming a laminate in which the green porcelain sheet is sandwiched by at least two or more conductive paste films, and firing the laminate in a non-oxidizing atmosphere And the process of
And a step of heat-treating the fired laminate in an oxidizing atmosphere.

Here, as the additive component, those of the invention of claim 1 (Li ₂ O-SiO ₂ -MO) and of the invention of claim 2 (B ₂ O ₃ -SiO ₂ -MO) are used. Either one of them may be used, and the non-oxidizing atmosphere may be not only a reducing atmosphere such as H ₂ or CO but also a neutral atmosphere such as N ₂ or Ar. Further, the firing temperature in the non-oxidizing atmosphere can be variously changed in consideration of the electrode material. When nickel is used as the internal electrode, it can be fired in the range of 1050 ° C to 1200 ° C with almost no agglomeration of nickel particles.

The temperature of the heat treatment in the oxidizing atmosphere may be lower than the firing temperature in the non-oxidizing atmosphere, and the range of 500 to 1000 ° C. is preferable.
The oxidizing atmosphere is not limited to the atmospheric atmosphere, and for example, an atmosphere having a low oxygen concentration such as a mixture of N ₂ and several ppm of O _{2 or} an atmosphere having an arbitrary oxygen concentration can be used. It is necessary to variously change the temperature and the oxygen concentration of the atmosphere in consideration of the oxidation of the electrode material (such as nickel) and the oxidation of the dielectric ceramic layer. In the examples described later, the temperature of this heat treatment is 60
Although the temperature is 0 ° C., it is not limited to this temperature.

Further, in Examples described later, firing in a non-oxidizing atmosphere and heat treatment in an oxidizing atmosphere are carried out in one step.
Although the steps are performed in one continuous profile, it is of course possible to perform the firing step in a non-oxidizing atmosphere and the heat treatment step in an oxidizing atmosphere in separate steps.

Further, although the Zn electrode is used as the external electrode in the embodiment, it is needless to say that an electrode made of Ni, Ag, Cu or the like can be used by selecting the baking condition of the electrode. It is also possible to apply an external electrode to the end surface of the unfired laminate and simultaneously fire the laminate and bake the external electrode.

The present invention can of course be applied to general single-layer porcelain capacitors other than laminated porcelain capacitors.

[0042]

EXAMPLES First, No. The case of sample No. 1 will be described. Preparation of Basic Components The compounds shown in Table 1 were each weighed, and these compounds were put in a pot mill together with a plurality of alumina balls and 2.5 liters of water, and mixed by stirring for 15 hours to obtain a mixture.

[0043]

[Table 1]

Here, the weight (g) of each compound in Table 1 is the composition formula ((Ba _1-vwx Ca _v Sr _w Mg _x ) O} _k (Ti _1-y Zr _y R _z ) O of the basic component. _{2-z / 2} + αM ₁ + βM ₂ (1) (where R is Sc, Y, Gd, Dy, Ho, Er, Y
one or more elements selected from b, Tb, Tm and Lu, M ₁ is P and / or V, M ₂ is Cr, Mn,
((Ba _1-vwx Ca _v Sr _w Mg _x ) O} _k (Ti) of the first term in one or more elements selected from Fe, Ni and Co)
_1-y Zr _y R _z ) O _{2-z / 2} is {(Ba _0.875 Ca _0.07 Sr _0.05 Mg _0.005 ) 0} _1.01 (Ti _0.83 Zr _0.15 Er
It is a value calculated and calculated to be _0.02 ) O _1.99 .

Next, this raw material mixture was placed in a stainless pot and dried at 150 ° C. for 4 hours using a hot air dryer, the dried mixture was roughly crushed, and the roughly crushed mixture was used in a tunnel furnace. About 1200 ℃ in the atmosphere
Then, the powder was calcined for 2 hours to obtain a powder of the component (first basic component) of the first item in the composition formula (1) of the basic component.

Then, with respect to the first basic component, 0.01
atom% (PO _5/2 is 0.031 g) of the second basic component (component of the second term αM ₁ in the composition formula (1) of the basic component),
1 atom% (CrO _3/2 is 3.274 g) of the third basic component (component of the third term βM ₂ in the composition formula (1) of the basic component)
Was weighed. Then, the weighed powders of all the basic components are mixed by stirring in a mixed pot mill, and the mixture is heated to 150 ° C.
And dried to obtain the powder of the basic component.

Preparation of Additive Components Further, the compounds shown in Table 2 were weighed out, and these compounds were placed in a polyethylene pot, a plurality of alumina balls and 30 parts.
The mixture was added with 0 ml of alcohol and mixed by stirring for 10 hours to obtain a mixture.

[0048]

[Table 2]

Here, the weight (g) of each compound in Table 2 is
Li ₂ O is 1 mol%, SiO ₂ is 80 mol%, MO is 1
It is a value calculated and calculated so as to have a composition of 9 mol% {BaO (3.8 mol%) + CaO (9.5 mol%) + MgO (5.7 mol%)}. Also, among MO, BaO,
The proportion of CaO and MgO is such that BaO is 20 mol%, CaO is 50 mol%, and MgO is 30 mol%.

Next, the mixture is heated to about 10% in the atmosphere.
It was calcined at a temperature of 00 ° C. for 2 hours, placed in an alumina pot together with a plurality of alumina balls and 300 ml of water, pulverized for 15 hours, and then dried at 150 ° C. for 4 hours to obtain an additive component of the above composition. A powder was obtained.

Preparation of Slurry Next, 100 parts by weight (1000 g) of the above basic components,
2 parts by weight (20 g) of the above-mentioned additional components were put into a ball mill, and further, 15% by weight of an organic binder and 50% by weight of water were added to the total weight of these basic components and additional components, and these were mixed. And pulverized to obtain a slurry as a raw material of the dielectric ceramic composition. Here, the organic binder used was an aqueous solution of acrylic acid ester polymer, glycerin and condensed phosphate.

Formation of Unsintered Porcelain Sheet Next, the above slurry was placed in a vacuum defoaming machine for defoaming treatment,
The defoamed slurry was applied on a polyester film with a reverse coater to a predetermined thickness, and the applied slurry was applied together with the polyester film to 1
It was heated at 00 ° C. and dried to obtain a long unsintered porcelain sheet having a thickness of about 18 μm. Then, this long unsintered porcelain sheet was cut to obtain a 10 cm square unsintered porcelain sheet.

Preparation and printing of conductive paste Also, 10 g of nickel powder having an average particle size of 1.5 μm, 0.9 g of ethyl cellulose and 9.1 g of butyl carbitol.
What was dissolved in was put in a stirrer and stirred for 10 hours,
A conductive paste for internal electrodes was obtained.

Then, 50 patterns (length 14 mm, width 7 mm) made of this conductive paste were formed on one surface of the green ceramic sheet by a screen printing method and dried.

Lamination of Unsintered Porcelain Sheets Next, two unsintered porcelain sheets were laminated with the side on which the pattern made of the conductive paste was formed facing up. At the time of this lamination, the patterns made of the conductive paste were shifted by about half in the longitudinal direction between the adjacent upper and lower unsintered porcelain sheets. Then, four unsintered porcelain sheets each having a thickness of 60 μm were laminated on each of the upper and lower surfaces of the laminated body as described above to obtain a laminated body.

Pressing and Cutting of Laminate Next, at a temperature of about 50 ° C., a load of about 40 tons is applied from the thickness direction to the laminate to form a green ceramic sheet constituting the laminate. We crimped each other. Then, this laminate was cut into a lattice shape to obtain 50 laminate chips.

Firing of Laminated Chip Next, the laminated chip is put into a furnace capable of atmospheric firing, the inside of the furnace is brought to an atmospheric atmosphere, the temperature is raised to 600 ° C. at a rate of 100 ° C./h, and unsintered. The organic binder in the porcelain sheet was burned and removed.

After that, the atmosphere in the furnace was changed from the air atmosphere to the reducing atmosphere {H ₂ (2% by volume) + N ₂ (98% by volume)}, and the temperature in the furnace was changed from 600 ° C. to 1160 ° C. to 100 ° C.
The temperature is raised at a rate of ° C / h, the temperature of 1160 ° C is maintained for 3 hours, and then the temperature is lowered at a rate of 100 ° C / h, the atmosphere in the furnace is changed to an atmospheric atmosphere (oxidizing atmosphere), and the temperature is set to 600 ° C.
The temperature was maintained for 30 minutes for oxidation treatment, and then cooled to room temperature to obtain a laminated sintered body chip.

Formation of External Electrodes Next, among the opposite side surfaces of this laminated sintered body chip,
By forming a pair of external electrodes on the side surfaces where the ends of the internal electrodes are exposed, as shown in FIG. 1, three dielectric ceramic layers 12,
A laminated ceramic capacitor 10 was obtained in which a pair of external electrodes 16, 16 were formed at the ends of a laminated sintered body chip 15 consisting of 12, 12 and two layers of internal electrodes 14, 14.

Here, the external electrode 16 is formed by applying a conductive paste composed of zinc, glass frit and vehicle to the side surface, drying the conductive paste, and then drying the conductive paste in the atmosphere at 550. The zinc electrode layer 18 is formed by baking at a temperature of ℃ for 15 minutes.
8 was formed by electroless plating, and then a Pb—Sn solder layer 22 was formed on the copper layer 20 by electroplating.

The thickness of the dielectric ceramic layer 12 of the laminated ceramic capacitor 10 is 0.012 mm, and the facing area of the pair of internal electrodes 14, 14 is 5 mm × 5 mm = 25 mm ² . The composition of the dielectric ceramic layer 12 after sintering is substantially the same as the composition of the mixture of the basic component and the additive component before sintering.

Measurement of Electrical Characteristics Next, the electrical characteristics of the laminated ceramic capacitor 10 are measured,
When the average value was obtained, as shown in Table 5, the relative permittivity ε _s was 14800, tan δ was 1.3%, and the resistivity ρ was
Is 3.25 × 10 ⁶ MΩ · cm, AC voltage characteristic tan δ
Was 2.9%.

The electrical characteristics were measured as follows. (A) The relative permittivity ε _s is measured by measuring the capacitance under the conditions of a temperature of 20 ° C., a frequency of 1 kHz, and a voltage (effective value) of 1.0 V. The measured value and the facing area of the pair of internal electrodes 14 and 14 (25
mm ² ), and the thickness (0.012 mm) of the dielectric ceramic layer 12 between the pair of internal electrodes 14, 14 was calculated. (B) Dielectric loss tan δ (%) is the relative permittivity ε
It was measured under the same conditions as in the case of _s measurement of. (C) The resistivity ρ (MΩ · cm) is D at a temperature of 20 ° C.
After applying C100V for 1 minute, a pair of external electrodes 1
The resistance value between Nos. 6 and 16 was measured and calculated based on the measured value and the dimension. (D) Dielectric loss tan δ at AC voltage of 200V / mm
(%) Was measured under the conditions of a temperature of 20 ° C., a frequency of 1 kHz, and a voltage (actual value) of 2.4 V.

As described above, No. The case of the sample of No. 1 was described, but No. Also in the case of the samples of Nos. 2 to 89, the composition of the basic component was changed as shown in Table 3 to Table 3, the composition of the added component was changed as shown in Table 4 to Table 4, and the firing temperature in the reducing atmosphere was changed. Other than changing as shown in Table 5 to Table 5, No. A laminated porcelain capacitor was prepared under exactly the same conditions as in the case of Sample 1, and the electrical characteristics were measured by the same method. No. The firing temperatures and electrical characteristics of the samples 1 to 89 are shown in Tables 5 to 5.

In Tables 3 to 3, 1-v-w-x
In the column of, the ratio of the number of Ba atoms in the first term of the composition formula of the basic component, in the column of v, the ratio of the number of Ca atoms in the first term of the composition formula of the basic component, and in the column of w, The ratio of the number of Sr atoms in the first term of the composition formula of the basic component is in the x column, the ratio of the number of Mg atoms in the first item of the composition formula of the basic component, and the 1-yz column is The ratio of the number of Ti atoms in the first term of the composition formula of the basic component, the y column is the ratio of the number of Zr atoms in the first term of the composition formula of the basic component, and the k column is the composition of the basic component. In the first term of the equation, {(Ba _1-vwx Ca _v Sr _w M
g _x ) O}, the proportion of the number of R atoms in the first term of the composition formula of the basic component in the z column, and the P and / of the second term in the composition formula of the basic component in the α column. Or, the ratio of the number of atoms of V is in the column of β, Cr, Mn of the third term in the composition formula of the basic component,
The ratio of the number of atoms of one or more elements selected from Fe, Ni and Co is shown.

In addition, in Tables 4 to 4, in the column of the content of the added component, in the column of the added amount by weight, the basic component 1 is added.
The addition amount of the additive component relative to 00 parts by weight is shown in parts by weight, and Li ₂ O, B ₂ O ₃ , SiO ₂ and M are shown in the composition column.
The proportion of O is shown in mol%, and the content of MO is indicated by Ba.
The proportion of O, SrO, CaO, MgO and ZnO is mol%
Indicated by.

Further, in Table 3 to Table 3, Table 4 to Table 4 and Table 5 to Table 5, No. Experiments using the samples 1 to 24 revealed the proper range of glass as an additive component, and No. The experiment using the samples of No. 25 to 30 clarified the appropriate range of the addition amount of the glass as the additive component, and No. 31
Experiments with ~ 36 samples are ratios of the number of Ca atoms v
Clarify the appropriate range of values, and Experiments using the samples of Nos. 37 to 52 clarified the appropriate ranges of the w value, which is the ratio of the number of Sr atoms, and the y value, which is the ratio of the number of Zr atoms, and No.
Experiments using samples Nos. 53 to 59 revealed an appropriate range of x value, which is the ratio of the number of Mg atoms, and No. Experiments with 60-66 samples revealed the effect of R type,
o. Experiments using the samples of Nos. 67 to 72 revealed a proper range of the z value, which is the ratio of the number of R atoms, and No. Experiments using the samples Nos. 73 to 77 revealed a proper range of the k value, which is the ratio of the {(Ba _1-vwx Ca _v Sr _w Mg _x ) O} component, and 78-83
The experiment with the sample of _{No. 1} revealed the appropriate range of the α value, which is the ratio of the number of atoms of M ₁ , and No. Experiments with samples 84-89 reveal the proper range of β values, which is the proportion of M ₂ atoms.

[0068]

[Table 3]

[0069]

[Table 3]

[0070]

[Table 3]

[0071]

[Table 3]

[0072]

[Table 3]

[0073]

[Table 3]

[0074]

[Table 4]

[0075]

[Table 4]

[0076]

[Table 4]

[0077]

[Table 4]

[0078]

[Table 4]

[0079]

[Table 4]

[0080]

[Table 5]

[0081]

[Table 5]

[0082]

[Table 5]

[0083]

[Table 5]

[0084]

[Table 5]

[0085]

[Table 5]

As is clear from the above results, according to the sample according to the present invention, 1200 in a non-oxidizing atmosphere.
By firing below ℃, relative dielectric constant ε _s is 7,000 or more, dielectric loss tan δ is 2.5% or less, and resistivity ρ is 1 × 10 ⁶ M
It is possible to obtain a porcelain capacitor provided with a dielectric porcelain composition having electrical characteristics of Ω · cm or more and an AC voltage characteristic tan δ of 5% or less.

On the other hand, in No. 6-8, 16-18,
25, 30, 36, 37, 42, 50, 52, 59, 6
According to the samples 7, 72, 73, 77, 78, 83, 84 and 89, it is not possible to obtain a porcelain capacitor having desired electrical characteristics. Therefore, these No. Samples are outside the scope of the present invention.

Next, the experiments shown in Table 3 to Table 3, Table 4 to Table 4 and Table 5 to Table 5 are given for the reason for limiting the composition range of the dielectric ceramic composition used in the ceramic capacitor according to the present invention. Explanation will be given with reference to the results.

First, the ratio of the number of Ca atoms in the composition formula of the basic component, that is, the value of v will be described. The value of v is the sample No. As shown in No. 35, in the case of 0.27, the dielectric porcelain composition having desired electrical characteristics can be obtained. As shown in 36, 0.3
In the case of 0, the firing temperature becomes as high as 1250 ° C., and the relative dielectric constant ε _s becomes worse as less than 7,000. Therefore, the upper limit value of v is 0.27.

Further, Ca has a function of flattening the temperature characteristics and a function of improving the resistivity ρ, but the value of v is the same as that of the sample No. As shown in 31, it is possible to obtain a dielectric porcelain composition having desired electrical characteristics even if it is zero. Therefore,
The lower limit value of v is zero.

Next, when the value of w, which is the ratio of the number of atoms of Sr in the composition formula of the basic component, and the value of y, which is the ratio of the number of atoms of Zr, are represented by the value of the relational expression 0.6w + y Will be described. The value of the relational expression 0.6w + y is the sample N
o. As shown in No. 43, when it is 0.05, the dielectric ceramic composition having desired electrical characteristics can be obtained. As shown in 37, in the case of 0.015, the relative permittivity ε _s becomes worse than less than 7,000. Therefore,
The lower limit value of the relational expression 0.6w + y is 0.05.

On the other hand, the value of the relational expression 0.6w + y is
o. As shown in Nos. 49 and 51, in the case of 0.260, a dielectric ceramic composition having desired electrical characteristics can be obtained, but Sample No. As shown in 50 and 52, 0.2
When the value exceeds 6 and becomes 0.290, the relative permittivity ε _s
Becomes less than 7,000. Therefore, the relational expression 0.6w +
The upper limit of y is 0.26.

However, the value of the relational expression 0.6w + y is 0.26.
Sample No. As shown in 42, when the value of w exceeds 0.37 and becomes 0.40, the relative permittivity ε _s becomes poor at less than 7,000. Therefore, the relational expression 0.6
The upper limit of w + y is 0.26, but at the same time, the upper limit of w must be 0.37.

Note that Sr and Zr represented by w and y have the same effect of shifting the Curie point to the low temperature side and increasing the relative dielectric constant at room temperature, and 0 ≦ w ≦ 0.37 and 0
<Y ≦ 0.26, and 0.05 ≦
It can be used in a range satisfying 0.6w + y ≦ 0.26.

Next, the ratio of the number of Mg atoms in the composition formula of the basic component, that is, the appropriate range of the value of x will be examined. The value of x is the sample No. As shown in 58, 0.03
In the case of No. 3, a dielectric ceramic composition having desired electrical characteristics can be obtained. As shown in 59, when it exceeds 0.03, the relative permittivity ε _s rapidly decreases to less than 7,000. Therefore, the upper limit of x is 0.03.

Further, Mg has a function of shifting the Curie point to the low temperature side, a function of flattening the temperature characteristic and a function of improving the resistivity ρ.
Even if it is 0 as shown in 53, it is possible to obtain a dielectric ceramic composition having desired electrical characteristics. Therefore, x
Is 0.

Next, the ratio of R in the composition formula of the basic component, that is, the value of z will be described. The value of z is the sample No. 68, when 0.002, a dielectric ceramic composition having desired electrical characteristics can be obtained. As shown in 67, in the case of 0.001, the dielectric loss tan δ is significantly deteriorated and the resistivity ρ is also deteriorated to less than 1 × 10 ⁴ MΩ · cm. Therefore, the lower limit value of z is 0.002.

On the other hand, the value of z is the sample No. 71, when 0.04, a dielectric ceramic composition having desired electrical characteristics can be obtained. 72
As shown in, when 0.06, the firing temperature is 125
A dense sintered body cannot be obtained even at 0 ° C. Therefore, the upper limit of z is 0.04.

The R component Sc, Y, Dy, Ho, E
r and Yb work almost in the same manner, and the same result can be obtained by using one or a plurality of them selected from these. In addition, among the R components, Lu is Table 3 to Table 3.
Although not described inside, this also has the same action and effect as other R components.

Next, the ratio of the number of atoms of M ₁ in the composition formula of the basic component, that is, the appropriate range of the value of α will be examined. The value of α is the sample No. As shown at 79, 0.0
In the case of No. 005, a dielectric porcelain composition having desired electrical characteristics can be obtained. As shown in 78, in the case of 0.0002, the AC voltage is 200 V / mm
Tan δ at 5.0% or more deteriorates. Therefore,
The lower limit of α is 0.0005.

On the other hand, the value of α is the value of the sample No. 82, when 0.01, a dielectric ceramic composition having desired electrical characteristics can be obtained. 83
As shown in, when 0.015, the resistivity ρ is 1 ×
It deteriorates to less than 10 ⁴ MΩ · cm. Therefore, the upper limit of α is 0.01.

It should be noted that P and V of the M ₁ component work almost in the same manner, and within the range of 0.0005 ≦ α ≦ 0.01,
One or both of P and V can be used.

Next, the ratio of the number of atoms of M ₂ in the composition formula of the basic component, that is, the appropriate range of the value of β will be examined. The value of β is the sample No. As shown at 85, 0.00
In the case of No. 05, it is possible to obtain a dielectric ceramic composition having desired electrical characteristics. As shown in 84, in the case of 0.0002, the AC voltage is 200 V / mm
Tan δ at 5.0% or more deteriorates. Therefore,
The lower limit of β is 0.0005.

On the other hand, the value of β is No. As shown in 88, when it is 0.01, a dielectric ceramic composition having desired electrical characteristics can be obtained. 89, when 0.015, the relative dielectric constant is 700.
It becomes worse when it is less than 0. Therefore, the upper limit of β is 0.01.

The M ₂ components of Cr, Mn, Fe, Ni
Each of Co and Co works almost in the same way, and the same effect can be obtained by using one selected from these or by using a plurality of them in combination.

Next, the preferable range of the additive component will be examined. First, when the additive component is a Li ₂ O-SiO ₂ -MO, preferred composition range of additional components, Li ₂ O-Si
It can be determined based on the triangle diagram of FIG. 2 showing the composition ratio of O ₂ —MO in mol%.

The first point A in this triangular diagram is the sample N.
o. As shown in FIG. 1, the composition of Li ₂ O is 1 mol%, SiO ₂ is 80 mol%, and MO is 19 mol%. 2, Li ₂ O has a composition of 1 mol%, SiO ₂ has a composition of 39 mol%, and MO has a composition of 60 mol%. As shown in 3,
₂ O 30 mol%, SiO ₂ 30 mol%, MO 40
The fourth point D indicates the sample No. As shown in FIG. 4, the composition of Li ₂ O is 50 mol%, SiO ₂ is 50 mol%, and MO is 0 mol%. As shown in Fig. 5, 20 mol% of Li ₂ O, SiO 2
₂ shows a composition of 80 mol% and MO of 0 mol%.

Sample No. As shown in FIGS. 1 to 5, the composition range of the additive component is the first to fifth points A to E of the triangular diagram (FIG. 2) showing the composition ratio of Li ₂ O—SiO ₂ —MO in mol% in order. The desired electrical characteristics can be obtained within the range surrounded by the five straight lines connecting the sample No. As shown in 6 to 8, if the composition of the additive component is out of the above range,
It is not possible to obtain a dense sintered body.

Next, the additive component is B ₂ O ₃ --SiO ₂ --M.
In the case of O, the preferable composition range of the additive component is B ₂ O ₃ −.
It can be determined based on the triangle diagram of FIG. 3 showing the composition ratio of SiO ₂ —MO in mol%.

The sixth point F in this triangular diagram is the sample N
o. As shown in FIG. 9, B ₂ O ₃ has a composition of 1 mol%, SiO ₂ has 80 mol%, and MO has a composition of 19 mol%. As shown in FIG. 10, B ₂ O ₃ has a composition of 1 mol%, SiO ₂ has a composition of 39 mol%, and MO has a composition of 60 mol%. As shown in 11,
₂ O ₃ 30 mol%, SiO ₂ 0 mol%, MO 70
The ninth point I indicates the sample No. 12, B ₂ O ₃ has a composition of 90 mol%, SiO ₂ is 0 mol%, and MO is 10 mol%. As shown in FIG. 14, 90% by mole of B ₂ O ₃ and S
The composition of 10 mol% of iO _{2 and} 0 mol% of MO is shown, and the eleventh point K is the sample No. As shown in 15, B ₂ O ₃
Is 20 mol%, SiO ₂ is 80 mol%, and MO is 0 mol%
The composition of

Sample No. As shown in 9 to 15, the composition range of the additive component is the sixth to eleventh points F to F of the triangular diagram (FIG. 3) showing the composition ratio of B ₂ O ₃ —SiO ₂ —MO in mol%.
The desired electrical characteristics can be obtained within the range surrounded by the six straight lines connecting K in order. 16-
As shown in No. 18, if the composition of the additive component is out of the above range, a dielectric ceramic composition having desired electrical characteristics cannot be obtained, or a dense sintered body cannot be obtained.

[0112]

According to the present invention, since the composition of the dielectric porcelain composition forming the dielectric layer of the porcelain capacitor is configured as described above, the composition in the non-oxidizing atmosphere is 120%.
Despite being fired at 0 ° C or lower, its relative dielectric constant ε
_s can be dramatically improved to 7200 to 18900, and therefore, there is an effect that the size and capacity of the porcelain capacitor can be reduced.

Further, according to the present invention, the composition of the dielectric porcelain composition forming the dielectric layer of the porcelain capacitor is configured as described above, so that a porcelain capacitor having a good AC voltage characteristic of dielectric loss can be obtained. There is an effect that can be obtained.

Furthermore, according to the present invention, since the dielectric ceramic composition forming the dielectric layer of the ceramic capacitor is sintered in a non-oxidizing atmosphere, the internal electrodes are made of an inexpensive base metal such as nickel. Since it can be formed with a conductive paste, the cost of the porcelain capacitor can be reduced in combination with the small size and large capacity of the porcelain capacitor.

[Brief description of drawings]

FIG. 1 is a sectional view of a laminated ceramic capacitor according to an embodiment of the present invention.

FIG. 2 is an additive component (Li ₂ O—SiO ₂ —M) of the dielectric composition forming the dielectric layer of the ceramic capacitor according to the present invention.
It is a triangular diagram showing a composition range of O).

FIG. 3 is an additive component (B ₂ O ₃ —SiO ₂ —M) of the dielectric composition forming the dielectric layer of the ceramic capacitor according to the present invention.
It is a triangular diagram showing a composition range of O).

[Explanation of symbols]

 12 Dielectric Ceramic Layer 14 Internal Electrode 15 Laminated Sintered Body Chip 16 External Electrode 18 Zinc Electrode Layer 20 Copper Layer 22 Pb-Sn Solder Layer

[Table 3 ○ 1]

[Table 3 ○ 2]

[Table 3 ○ 3]

[Table 3-4]

[Table 3-5]

[Table 3 ○ 6]

[Table 4 ○ 1]

[Table 4 ○ 2]

[Table 4 ○ 3]

[Table 4 ○ 4]

[Table 4-5]

[Table 4-6]

[Table 5 ○ 1]

[Table 5 ○ 2]

[Table 5 ○ 3]

[Table 5 ○ 4]

[Table 5 ○ 5]

[Table 5 ○ 6]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mutsumi Honda 6-16-20 Ueno, Taito-ku, Tokyo Within Taiyo Electric Co., Ltd. (72) Hiroshi Kishi 6-16-20 Ueno, Taito-ku, Tokyo Within Taiyo Electric Co., Ltd.

Claims (4)

[Claims] 1. A ceramic capacitor comprising one or more dielectric porcelain layers made of a dielectric porcelain composition and at least two or more internal electrodes sandwiching the dielectric porcelain layer, wherein the dielectric The porcelain composition is formed by firing a mixture of 100.0 parts by weight of the basic component and 0.2 to 5.0 parts by weight of the additive component, and the basic component is {(Ba _1-vwx Ca _v Sr _w Mg _x ) O} _k (Ti _1-yz Zr
_y R _z ) O _{2-z / 2} + αM ₁ + βM ₂ (where R is Sc, Y, G
one or more elements selected from d, Dy, Ho, Er, Yb, Tb, Tm and Lu, M ₁ is P and / or V, M ₂ is Cr, Mn, Fe, Ni, Co One or more selected elements, v, w, x, y, z,
k, α and β are 0.00 ≦ v ≦ 0.27 0.00 ≦ w ≦ 0.37 0.00 ≦ x ≦ 0.03 0.00 <y <0.26 0.05 ≦ 0.6w + y ≦ 0.26 0.002 ≦ z ≦ 0.04 1.00 ≦ k ≦ 1.04 0.0005 ≦ α ≦ 0.01 0.0005 ≦ β ≦ 0.01) The additive components are Li ₂ O, SiO ₂ and MO (however, MO
Is one kind or two or more kinds of oxides selected from BaO, SrO, CaO, MgO and ZnO), and the composition range of Li ₂ O, SiO ₂ and MO is % Of the Li ₂ O, 80 mol% of the SiO ₂ ,
A first point A showing a composition of MO of 19 mol%, Li ₂ O of 1 mol%, SiO ₂ of 39 mol%,
A second point B showing a composition of MO of 60 mol%, and a third point C showing a composition of 30 mol% of Li ₂ O, 30 mol% of SiO _{2, and} 40 mol% of MO. A fourth point D showing a composition of 50 mol% of Li ₂ O, 50 mol% of SiO _{2, and} 0 mol% of MO, 20 mol% of Li ₂ O, and 80 mol of SiO ₂ %, The MO is in a region surrounded by five straight lines connecting the fifth point E indicating the composition of 0 mol% in this order, and a ceramic capacitor. 2. A porcelain capacitor comprising one or more dielectric porcelain layers made of a dielectric porcelain composition, and at least two or more internal electrodes sandwiching the dielectric porcelain layer. The porcelain composition is formed by firing a mixture of 100.0 parts by weight of the basic component and 0.2 to 5.0 parts by weight of the additive component, and the basic component is {(Ba _1-vwx Ca _v Sr _w Mg _x ) O} _k (Ti _1-yz Zr
_y R _z ) O _{2-z / 2} + αM ₁ + βM ₂ (where R is Sc, Y, G
one or more elements selected from d, Dy, Ho, Er, Yb, Tb, Tm and Lu, M ₁ is P and / or V, M ₂ is Cr, Mn, Fe, Ni, Co One or more selected elements, v, w, x, y, z,
k, α and β are 0.00 ≦ v ≦ 0.27 0.00 ≦ w ≦ 0.37 0.00 ≦ x ≦ 0.03 0.00 <y <0.26 0.05 ≦ 0.6w + y ≦ 0.26 0.002 ≦ z ≦ 0.04 1.00 ≦ k ≦ 1.04 0.0005 ≦ α ≦ 0.01 0.0005 ≦ β ≦ 0.01) The additive components are B ₂ O ₃ , SiO ₂ and MO (however, MO is
Is one or more oxides selected from BaO, SrO, CaO, MgO and ZnO), and the composition range of B ₂ O ₃ , SiO ₂ and MO is In the triangle diagram shown by mol%, the B ₂ O ₃ is 1 mol%, the SiO ₂ is 80 mol%,
A sixth point F having a composition of MO of 19 mol%, 1 mol% of B ₂ O _{3 and} 39 mol% of SiO ₂ .
A seventh point G showing a composition of MO of 60 mol%, B ₂ O ₃ of 30 mol%, SiO ₂ of 0 mol%,
An eighth point H indicating a composition of MO of 70 mol%, B ₂ O ₃ of 90 mol%, SiO ₂ of 0 mol%,
A ninth point I showing a composition of MO of 10 mol%, and a tenth point J showing a composition of 90 mol% of B ₂ O _3, 10 mol% of SiO ₂ , and 0 mol% of MO. And a region surrounded by six straight lines connecting in this order the eleventh point K indicating the composition of 20 mol% of B ₂ O _3, 80 mol% of SiO _{2 and} 0 mol% of MO. A porcelain capacitor characterized by being inside. 3. A step of preparing a mixture of unsintered porcelain powder, a step of forming an unsintered porcelain sheet of the mixture, and a step of forming at least two or more conductive paste films of the unsintered porcelain sheet. And a step of firing the laminate in a non-oxidizing atmosphere, and a step of heat-treating the fired laminate in an oxidizing atmosphere. The mixture composed of the porcelain powder for binding comprises 100.0 parts by weight of the basic component and 0.2 to 5.0 parts by weight of the additional component, and the basic component is {(Ba _1-vwx Ca _v Sr _w Mg _x ) O} _k (Ti _1-yz Zr
_y R _z ) O _{2-z / 2} + αM ₁ + βM ₂ (where R is Sc, Y, G
one or more elements selected from d, Dy, Ho, Er, Yb, Tb, Tm and Lu, M ₁ is P and / or V, M ₂ is Cr, Mn, Fe, Ni, Co One or more selected elements, v, w, x, y, z,
k, α and β are 0.00 ≦ v ≦ 0.27 0.00 ≦ w ≦ 0.37 0.00 ≦ x ≦ 0.03 0.00 <y <0.26 0.05 ≦ 0.6w + y ≦ 0.26 0.002 ≦ z ≦ 0.04 1.00 ≦ k ≦ 1.04 0.0005 ≦ α ≦ 0.01 0.0005 ≦ β ≦ 0.01) The additive components are Li ₂ O, SiO ₂ and MO (however, MO
Is one kind or two or more kinds of oxides selected from BaO, SrO, CaO, MgO and ZnO), and the composition range of Li ₂ O, SiO ₂ and MO is % Of the Li ₂ O, 80 mol% of the SiO ₂ ,
A first point A showing a composition of MO of 19 mol%, Li ₂ O of 1 mol%, SiO ₂ of 39 mol%,
A second point B showing a composition of MO of 60 mol%, and a third point C showing a composition of 30 mol% of Li ₂ O, 30 mol% of SiO _{2, and} 40 mol% of MO. A fourth point D showing a composition of 50 mol% of Li ₂ O, 50 mol% of SiO _{2, and} 0 mol% of MO, 20 mol% of Li ₂ O, and 80 mol of SiO ₂ %, The MO is in a region surrounded by five straight lines connecting the fifth point E indicating the composition of 0 mol% in this order, and a method for manufacturing a porcelain capacitor. 4. A step of preparing a mixture made of unsintered porcelain powder, a step of forming an unsintered porcelain sheet made of the mixture, and at least two or more conductive paste films formed from the unsintered porcelain sheet. And a step of firing the laminate in a non-oxidizing atmosphere, and a step of heat-treating the fired laminate in an oxidizing atmosphere. The mixture composed of the porcelain powder for binding comprises 100.0 parts by weight of the basic component and 0.2 to 5.0 parts by weight of the additional component, and the basic component is {(Ba _1-vwx Ca _v Sr _w Mg _x ) O} _k (Ti _1-yz Zr
_y R _z ) O _{2-z / 2} + αM ₁ + βM ₂ (where R is Sc, Y, G
one or more elements selected from d, Dy, Ho, Er, Yb, Tb, Tm and Lu, M ₁ is P and / or V, M ₂ is Cr, Mn, Fe, Ni, Co One or more selected elements, v, w, x, y, z,
k, α and β are 0.00 ≦ v ≦ 0.27 0.00 ≦ w ≦ 0.37 0.00 ≦ x ≦ 0.03 0.00 <y <0.26 0.05 ≦ 0.6w + y ≦ 0.26 0.002 ≦ z ≦ 0.04 1.00 ≦ k ≦ 1.04 0.0005 ≦ α ≦ 0.01 0.0005 ≦ β ≦ 0.01) The additive components are B ₂ O ₃ , SiO ₂ and MO (however, MO is
Is one or more oxides selected from BaO, SrO, CaO, MgO and ZnO), and the composition range of B ₂ O ₃ , SiO ₂ and MO is In the triangle diagram shown by mol%, the B ₂ O ₃ is 1 mol%, the SiO ₂ is 80 mol%,
A sixth point F having a composition of MO of 19 mol%, 1 mol% of B ₂ O _{3 and} 39 mol% of SiO ₂ .
A seventh point G showing a composition of MO of 60 mol%, B ₂ O ₃ of 30 mol%, SiO ₂ of 0 mol%,
An eighth point H indicating a composition of MO of 70 mol%, B ₂ O ₃ of 90 mol%, SiO ₂ of 0 mol%,
A ninth point I showing a composition of MO of 10 mol%, and a tenth point J showing a composition of 90 mol% of B ₂ O _3, 10 mol% of SiO ₂ , and 0 mol% of MO. And a region surrounded by six straight lines connecting in this order the eleventh point K indicating the composition of 20 mol% of B ₂ O _3, 80 mol% of SiO _{2 and} 0 mol% of MO. A method of manufacturing a porcelain capacitor, characterized in that