JP3269910B2 - Porcelain capacitor and method of manufacturing the same - Google Patents

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 multilayer structure in which one or more dielectric ceramic layers are sandwiched by at least two or more internal electrodes, and a method of manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, the following method has been used for manufacturing a laminated ceramic capacitor. That is, a ceramic green sheet is prepared by a doctor blade method or the like, a paste of metal powder to be used as an internal electrode is printed on the green sheet, a plurality of these are stacked and thermocompressed, and fired in a natural atmosphere of 1300 ° C. or more. In this way, a sintered body was produced, and an external electrode that is electrically connected to the internal electrode was baked on the end face of the sintered body.

[0003] Here, noble metals such as palladium, platinum and silver-palladium do not oxidize upon contact with the ceramic or directly react with the ceramic even under the above-mentioned manufacturing conditions. It was used for porcelain capacitors, but was expensive and was the biggest cause of high cost.

As a means for solving such a problem, an attempt has been made to use a base metal as the material of the internal electrode. However, if, for example, nickel is used as the material of the internal electrode, it is oxidized by firing in a natural atmosphere and easily reacts with the ceramic, so that the internal electrode cannot be formed. In order to prevent such oxidation of the base metal, firing must be performed in a reducing atmosphere. However, when firing is performed in a reducing atmosphere, the ceramic is significantly reduced and does not function as a capacitor.

In order to solve such a problem, the present applicant has proposed a number of dielectric ceramic compositions as disclosed in the following publication.

For example, JP-A-5-270904 discloses (1−α) ((Ba _{k− (x + y)} M _x L _y ) O _k TiO ₂ + α (R _1−z R ′ _z ) O
_3/2 (where M is Mg and / or Zn, L is Ca and / or
Or Sr and R are one or more elements selected from La, Ce, Pr, Nd, Pm, Sm and Eu, and R 'is selected from Sc, Y, Gd, Dy, Ho, Er and Yb. A basic component consisting of one or more elements)
i ₂ O, SiO ₂ and MO (where MO is BaO, Ca
A dielectric porcelain composition comprising an additional component comprising one or more oxides selected from O and SrO) is disclosed.

Japanese Patent Application Laid-Open No. Hei 5-270905 discloses that (1-α) (Ba _{k− (x + y)} M _x L _y ) O _k TiO ₂ + α (R _1−z R ′ _z ) O _3/2
(However, M is Mg and / or Zn, L is Ca and / or Sr, R is La, Ce, Pr, Nd, Pm, Sm and E
one or more elements selected from u, R ′ is S
one or more elements selected from c, Y, Gd, Dy, Ho, Er and Yb), and B ₂
O ₃ , SiO ₂ and MO (where MO is BaO, CaO
And one or more oxides selected from SrO)
And an additive component comprising:

[0008] These disclosed dielectric porcelain compositions can be used to produce porcelain capacitors by firing at 1200 ° C or lower in a non-oxidizing atmosphere, and have a relative dielectric constant of 30.
00, dielectric loss tan δ is 2.5% or less, resistivity ρ
Is not less than 4 × 10 ⁶ MΩ · cm, and the temperature change rate of the relative dielectric constant is −15% to + 15% at −55 ° C. to 125 ° C.
(Based on 25 ° C), -10% + 10 at -25 ° C to 85 ° C
% (Based on 20 ° C.).

[0009]

In recent years, as electronic circuits have become smaller and more dense, there has been a strong demand for small and large-capacity porcelain capacitors. As one of the methods, a laminated ceramic capacitor is known, and attempts have been made to increase the capacity by reducing the thickness of the dielectric green sheet or increasing the number of layers. However, in the laminated ceramic capacitor, making the dielectric ceramic layer thinner increases the AC voltage per unit thickness and increases the dielectric loss (tan δ). Therefore, an object of the present invention is to provide a ceramic capacitor provided with a dielectric ceramic composition having better AC voltage characteristics of dielectric loss than the dielectric ceramic compositions disclosed in the above publications.

[0010]

According to the first and second aspects of the present invention, there are provided one or more dielectric ceramic layers comprising a dielectric ceramic composition, A ceramic capacitor comprising at least two internal electrodes sandwiched therebetween, wherein the dielectric ceramic composition comprises:
A mixture of 00.0 parts by weight of a basic component and 0.2 to 5.0 parts by weight of an additive component is calcined, and the basic component is represented by the formula (1−γ) (Ba _{k− (x + y )} M _x L _y ) O _k TiO ₂ + γ (R _1-z R ' _z ) O
_3/2 + αAO _5/2 + βD (where M is Mg and / or Zn, L
Is Ca and / or Sr, R is La, Ce, Pr, Nd,
One or more elements selected from Pm, Sm and Eu, and R 'is Sc, Y, Gd, Tb, Dy, Ho, E
one or more elements selected from r, Tm, Yb and Lu, A is P and / or V, D is Cr, Mn, F
e, one or more oxides selected from Co and Ni, α, β, γ, k, x, y and z are 0.0005 ≦ α ≦ 0.01 0.0005 ≦ β ≦ 0 .01 0.002 ≦ γ ≦ 0.06 1.00 ≦ k ≦ 1.05 0 ≦ x <0.10 0 ≦ y ≦ 0.05 0.01 ≦ x + y ≦ 0.10 0.5 ≦ z ≦ 0 .9 that satisfies .9).

Here, the ratio of the component A in the composition formula of the basic component, that is, the value of α is 0.0005 ≦ α ≦ 0.
A range of 01 is preferred. When the value of α is less than 0.0005, the dielectric loss tan δ at an AC voltage of 200 V / mm
Exceeds 3.0%, and when the value of α exceeds 0.01, the resistivity ρ becomes smaller than 4.0 × 10 ⁶ MΩ · cm, and the temperature change rate of the capacitance _{ C ₋₅₅ , △ _} . C ₁₂₅ is -15
% To + 15%, △ C _-25 and △ C ₈₅ are -10% to
Although it deviates from + 10%, the value of α is 0.0005 ≦
This is because a material having desired electric characteristics can be obtained in the range of α ≦ 0.01.

Incidentally, P and V of the A component work almost in the same way,
P and V in a range satisfying 0.0005 ≦ α ≦ 0.01
One or both can be used.

The ratio of the D component in the composition formula of the basic component, that is, the value of β is 0.0005 ≦ β ≦ 0.0
A range of 1 is preferred. If the value of β is less than 0.0005,
The dielectric loss tan δ at an AC voltage of 200 V / mm exceeds 3.0%, and when the value of β exceeds 0.01, the relative dielectric constant becomes smaller than 3300.
This is because in the range of 005 ≦ β ≦ 0.01, one having desired electrical characteristics can be obtained.

The D components, Cr, Mn, Fe, C
The oxides of o and Ni work almost in the same way, and the same effect can be obtained by using one selected from these or by using a combination of two or more.

The value of γ in the composition formula of the basic component is preferably in the range of 0.002 ≦ γ ≦ 0.06. When the value of γ is less than 0.002, the temperature change rate of the capacitance ΔC
_-55 deviates from -15% to + 15%, ΔC _{-25 decelerates} to -10
% To + 10%, and the value of γ is 0.06
If it exceeds, a dense sintered body cannot be obtained,
When the value of γ is in the range of 0.002 ≦ γ ≦ 0.06, a dense sintered body having desired electric characteristics can be obtained.

The value of k is 1.00 ≦ k ≦ 1.05
Is preferable. When the value of k is less than 1.00, the resistivity ρ becomes smaller than 4.0 × 10 ⁶ MΩ · cm, and the temperature change rates ΔC ₋₅₅ and ΔC _{125 of the} capacitance become −15% to +15.
%, ΔC _-25 and ΔC ₈₅ deviate from −10% to + 10%, and if the value of k exceeds 1.05, a dense sintered body cannot be obtained. Value is 1.0
This is because a dense sintered body having desired electrical characteristics can be obtained in the range of 0 ≦ k ≦ 1.05.

The value of x + y is 0.01 ≦ x + y ≦
A range of 0.10 is preferred. If the value of x + y is less than 0.01, the temperature change rate ΔC _{−55 of the} capacitance is −15% to +1.
When the value of x + y exceeds 0.10 and the value of x + y exceeds 0.10, the temperature change rate ΔC _{85 of the} capacitance deviates from −10% to + 10%, but the value of x + y is 0.010 ≦ x + y ≦ 0. .1
This is because in the range of 0, a dense sintered body having desired electric characteristics can be obtained.

However, even if x + y ≦ 0.10, y
≦ 0.05 is preferred. This is because, even if x + y ≦ 0.10 is satisfied, when the value of y exceeds 0.05, the temperature change rate ΔC _{85 of the} capacitance deviates from −10% to + 10%.

Incidentally, Mg and Zn of the M component and C and C of the L component
a and Sr work almost in the same way, and use one or both of Mg and Zn in a range satisfying 0 ≦ x ≦ 0.10, and Ca and Sr in a range satisfying 0 ≦ y ≦ 0.05.
One or both can be used.

The value of z is preferably in the range of 0.5 ≦ z ≦ 0.9. When the value of z is less than 0.5, tan δ is 2.
5%, the dielectric loss tan δ at an AC voltage of 200 V / mm exceeds 3.0%, and the resistivity ρ
Becomes smaller than 4.0 × 10 ⁶ MΩ · cm, and the temperature change rate ΔC- _{55 of the} capacitance deviates from −15% to + 15%.
When ΔC _-25 and ΔC ₈₅ deviate from -10% to + 10% and the value of z exceeds 0.9, the relative dielectric constant becomes 3300 or less. This is because in the range, a material having desired electric characteristics can be obtained.

The R components La, Ce, Pr, Nd,
Pm, Sm and Eu, and R, component Sc, Y, G
Each of d, Tb, Dy, Ho, Er, Tm, Yb and Lu works almost in the same way, and the same result can be obtained by using one selected from these or by using a plurality of them. Things.

However, the value of z is determined as follows when the R component and the R ′ component are each one kind or plural kinds.
It is desirable to set the range of 0.5 ≦ z ≦ 0.9.

The basic components x, y, z and k are the number of atoms of each element in the composition formula of the basic component, ie, T
The ratio of the number of atoms of each element when the number of atoms of i is 1 is shown. Α and β are the number of atoms of each oxide in the above-described basic component composition formula, that is, (1−γ) (Ba _{k− (x + y)} M _× L _y ) O _k TiO ₂ + γ (R _1-z R ' _z ) O
The ratio of the number of atoms of each oxide when the number of molecules of _3/2 is 1 is shown.

The starting materials for obtaining the basic components are
For example, BaO, SrO, C other than those shown in the embodiment
An oxide such as aO, a hydroxide, or another compound may be used.

Next, as an additive component, Li ₂ O—Si
Either or both of O ₂ -MO and B ₂ O ₃ -SiO ₂ -MO can be used. The addition amount of the additional component is preferably in the range of 0.2 to 5 parts by weight based on 100 parts by weight of the basic component. If the amount of the additional component is less than 0.2 parts by weight, a dense sintered body cannot be obtained even at a firing temperature of 1250 ° C., and the amount of the additional component exceeds 5 parts by weight. Has a relative dielectric constant of less than 3300, and the temperature change rate ΔC _{−55 of the} capacitance deviates from −15% to + 15%, but when the additive component is in the range of 0.2 to 5 parts by weight, This is because a dense sintered body having desired electric characteristics can be obtained.

According to the first aspect of the present invention, the additive component is Li ₂ O, SiO ₂ and MO (where MO is Ba).
O, it becomes from SrO, CaO, 1 or more kinds of oxide selected from MgO and ZnO) and the Li ₂ O
In the triangular diagram in which the composition range of SiO ₂ and MO is represented by mol%, the composition is 1 mol% of Li ₂ O, 80 mol% of SiO ₂ , and 19 mol% of MO. And the first point A indicating that the Li ₂ O is 1 mol%, the SiO ₂ is 39 mol%, and the MO is 60 mol%
A second point B indicating the composition of the above, and the Li ₂ O is 30 mol%, the SiO ₂ is 30 mol%, and the MO is 40 mol%
A third point C indicating the composition of the Li ₂ O is 50 mol%, the SiO ₂ is 50 mol%, and D fourth points indicating the MO composition of 0 mol%, the Li ₂ O is 20 mol%,
A region surrounded by five straight lines connecting a fifth point E having a composition of 80 mol% of SiO _{2 and} 0 mol% of MO in this order.

Here, the composition of the additive component is Li ₂ O—S
In the triangular diagram showing the composition ratio of iO ₂ -MO in mol%,
The points A to E are set in a region surrounded by five straight lines connecting in this order, provided that the composition of the additive component is within this range, the dielectric ceramic composition having desired electric characteristics. This is because if the composition of the additive component is out of this range, a dense sintered body cannot be obtained even at 1250 ° C. firing. The MO component BaO,
SrO, CaO, MgO and ZnO may be used in an appropriate ratio. The starting material of the additional component may be another compound such as an oxide or a hydroxide.

Further, the invention according to claim 2 is characterized in that the additional components are B ₂ O ₃ , SiO ₂ and MO (where MO is BaO,
Becomes because SrO, CaO, 1 or two or more metal oxide selected from MgO and ZnO) and, the B ₂ O ₃
0 is 1 mol%, the SiO ₂ is 80 mol%, the MO is 19 mol%, a sixth point F indicating the composition, the B ₂ O ₃ is 1 mol%, the SiO ₂ is 39 mol%, MO is 60
A seventh point G indicating a mole% composition, and the B ₂ O ₃
An eighth point H having a composition of 1 mol% of SiO ₂ , 1 mol% of SiO _{2 and} 70 mol% of MO, 90 mol% of B ₂ O _3, 1 mol% of SiO ₂ , and 9 mol of MO A ninth point I indicating a composition of 90% by mole, a tenth point J indicating a composition of 90% by mole of B ₂ O _3, 9% by mole of SiO _{2, and} 1% by mole of MO; 19% by mole of ₂ O ₃
This is in a region surrounded by six straight lines connecting in this order an eleventh point K having a composition of 80 mol% of O _{2 and} 1 mol% of MO.

Here, the composition of the additive component is represented by B ₂ O ₃ —S
In the triangular diagram showing the composition ratio of iO ₂ -MO in mol%,
The points F to K were set in the region surrounded by the six straight lines connecting in this order, as long as the composition of the additive component was within this range, the dielectric ceramic composition having desired electric characteristics was obtained. This is because if the composition of the additive component is out of this range, a dense sintered body cannot be obtained even at 1250 ° C. firing. The MO component BaO,
SrO, CaO, MgO and ZnO may be used in an appropriate ratio. The starting material of the additional component may be another compound such as an oxide or a hydroxide.

The invention according to claims 3 and 4 for solving the above-mentioned problems is characterized in that a step of preparing a mixture comprising a non-sintered porcelain powder comprising the above-mentioned basic components and additional components, Forming a non-sintered porcelain sheet, forming a laminate in which the non-sintered porcelain sheet is sandwiched between at least two or more conductive paste films, and firing the laminate in a non-oxidizing atmosphere. The process of
Heat-treating the fired laminate in an oxidizing atmosphere.

Here, as the additional components, those of the invention according to claim 1 (Li ₂ O—SiO ₂ —MO) and those of the invention according to claim 2 (B ₂ O ₃ —SiO ₂ —MO) Either or both can be used. Further, 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. 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, firing can be performed at a temperature in the range of 1050 ° C. to 1200 ° C. with almost no aggregation of nickel particles.

The heat treatment temperature in the oxidizing atmosphere may be lower than the firing temperature in the non-oxidizing atmosphere, and is preferably in the range of 500 ° C. to 1000 ° C.
The oxidizing atmosphere is not limited to the air atmosphere, but may be an atmosphere having a low oxygen concentration such as a mixture of N ₂ and O ₂ of several ppm, and an atmosphere having an arbitrary oxygen concentration. What kind of temperature or what kind of oxygen concentration the atmosphere should be changed in various ways in consideration of oxidation of the electrode material (nickel or the like) and oxidation of the dielectric ceramic layer. In the embodiment described later, the temperature of this heat treatment is set to 60.
Although the temperature was set to 0 ° C., the temperature is not limited to this.

In the embodiments described later, the heat treatment in the non-oxidizing atmosphere and the heat treatment in the oxidizing atmosphere are performed in one continuous firing profile. And a heat treatment step in an oxidizing atmosphere can be performed separately.

In the embodiments described later, a Zn electrode is used as an external electrode. However, an electrode made of Ni, Ag, Cu, or the like can be used by selecting electrode baking conditions. It is also possible to apply electrodes to the end surfaces of the unsintered laminate, and to simultaneously bake the laminate and bake the external electrodes.

The present invention can of course be applied to general single-layer ceramic capacitors other than the multilayer ceramic capacitor.

[0036]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below mainly on the case of the sample No. 1. First, BaCO ₃ , MgO,
ZnO, CaCO ₃ , SrCO ₃ , TiO ₂ and Er ₂
O ₃ was weighed as shown in Table 1.

[0037]

[Table 1]

Here, the weight of each compound in Table 1 is determined by the composition formula (1-γ) (Ba _{k− (x + y)} M _x L _y ) O _k TiO ₂ + γ (R
_1-z R ′ _z ) O _3/2 + αAO _5/2 + βD (B) of the first term in (1)
a _{k- (x + y)} M _x L _y ) O _k TiO ₂ … (2) is (Ba _0.96 Mg _0.03 Zn _0.01 C
a _0.01 Sr _{0.0 1} ) O _1.02 TiO ₂ ... (3) In addition, as each of these compounds, 9
Those having a purity of 9.0% or more were used.

Next, these compounds were put into a ball mill together with 2.5 liters of water, mixed for about 20 hours by a wet method, dried at 150 ° C. for 4 hours, and then pulverized. For 2 hours to obtain the component powder of the first item of the composition formula (1).

Next, 185.61 powder of Sm ₂ O ₃ was added.
g, and powder 814.39g weighed of Er ₂ O _3, these were mixed for about 20 hours in a ball mill, and pulverized after drying for 4 hours at 0.99 ° C., the second term in the above composition formula (1) (R _1-z R ′) O _3/2 (4) is (Sm _0.2 Er)
_0.8 ) O _3/2 ... (5) powder was obtained.

Then, 982.44 g (98 mol parts) of the component powder of the first term of the composition formula (1), 16.33 g (2 mol parts) of the component powder of the second term, and the component (3) of the third term ( PO
_5/2 ) 0.62 g (0.2 mol parts) of the powder and 0.62 g (0.2 mol parts) of the component (MnO) powder of the fourth item were mixed in a wet system, and dried at 150 ° C. A powder of a basic component in which the component of the first term is represented by 0.98 mol, the component of the second term is represented by 0.02 mol, the component of the third term is represented by 0.002 mol, and the component of the fourth term is represented by 0.002 mol. I got

On the other hand, Li ₂ O, SiO ₂ , CaCO ₃ ,
SrCO ₃ and BaCO ₃ were each weighed as shown in Table 2.

[0043]

[Table 2]

Here, the weights of the compounds in Table 2 are based on the additive components: 30 mol% of Li ₂ O, 60 mol% of SiO ₂ , 10 mol% of MO ｛CaO (8 mol%), SrO
(1 mol%) and BaO (1 mol%)}. Each of these compounds had a purity of 99.0% or more.

Next, each of these compounds was put in a polyethylene pot together with 300 cc of alcohol and mixed for about 10 hours, and then calcined in the air at 1000 ° C. for 2 hours. Put in an alumina pot with alcohol, pulverize with alumina balls for 15 hours, then dry at 150 ° C. for 4 hours,
A powder of the additional component was obtained.

Next, 1000 g of powder of the basic component (100
10 parts by weight (1 part by weight) of the above-mentioned additive component, and an organic binder composed of an aqueous solution of an acrylate polymer, glycerin and a condensed phosphate to the total weight of the basic component and the additive component. 15% by weight
Then, 50% by weight of water was added, and the mixture was put in a ball mill and pulverized and mixed to prepare a slurry of a porcelain raw material.

Next, the slurry is put into a vacuum defoamer to remove bubbles, the slurry is put into a reverse roll coater, and a thin film based on the slurry is formed on a polyester film using the slurry. 1 on film
The resultant was heated to 00 ° C. and dried to obtain a green sheet having a thickness of about 20 μm. This sheet was punched into a 10 cm square square for use.

On the other hand, as the conductive paste for the internal electrode, 10 g of nickel powder having an average particle size of 1.5 μm and a solution prepared by dissolving 0.9 g of ethyl cellulose in 9.1 g of butyl carbitol were placed in a stirrer, and the mixture was stirred for 10 hours Obtained by stirring. This conductive paste was printed on one side of the green sheet through a screen having 50 patterns having a length of 14 mm and a width of 7 mm, and then dried.

Next, two green sheets were laminated with the printed side facing up. At this time, the printing surfaces of the adjacent upper and lower sheets were arranged so as to be shifted by about half in the longitudinal direction of the pattern. Furthermore, unprinted green sheets were laminated on each of the upper and lower surfaces of the laminate by 10 sheets each. Next, the laminate was pressed at a temperature of about 50 ° C. by applying a pressure of about 40 tons in the thickness direction. Thereafter, the laminate was cut into a lattice to obtain about 50 laminated chips.

Next, the laminated chip was placed in a furnace capable of atmosphere and heated to 600 ° C. in the atmosphere at a rate of 100 ° C./hr to burn the organic binder. Thereafter, the atmosphere of the furnace was changed from the atmosphere to an atmosphere of H ₂ (2% by volume) + N ₂ (98% by volume). Then, while maintaining the furnace in the reducing atmosphere as described above, the heating temperature of the laminated body chip was raised from 600 ° C. to the firing temperature of 1150 ° C. (maximum temperature) by 3.
After holding for a period of time, the temperature was lowered to 600 ° C. at a rate of 100 ° C./hr, the atmosphere was replaced with an air atmosphere (oxidizing atmosphere), the oxidation treatment was performed at 600 ° C. for 30 minutes, and then cooled to room temperature. Thus, a sintered chip was obtained.

Next, a conductive paste composed of zinc, glass frit and vehicle is applied to the side surface of the sintered chip where the electrodes are exposed, dried and baked at 550 ° C. for 15 minutes in the air. A zinc electrode layer was formed, copper was further applied thereon by electroless plating, and a Pb-Sn solder layer was further provided thereon by electroplating to form a pair of external electrodes.

As a result, as shown in FIG. 1, a laminated ceramic capacitor 10 comprising the dielectric ceramic layer 12, the internal electrode 14, and the external electrode 16 was obtained. The thickness of the dielectric ceramic layer 12 of the capacitor 10 is 0.015 mm, and the opposing area of the internal electrodes is 5 mm × 5 mm = 25 mm ² . The composition of the dielectric ceramic layer 12 after sintering is substantially the same as the mixed composition of the basic component and the additive component before sintering.

Next, when the electrical characteristics of the completed laminated ceramic capacitor were measured, as shown in the column of Sample No. 1 in Table 6, the relative dielectric constant ε _s was 3380 and tan δ was 1.6.
%, Resistivity 5.7 × 10 ⁶ MΩ · cm, AC voltage 2
The tan δ at 00 V / mm is 2.1%, and the capacitance change rates ΔC ₋₅₅ and ΔC _{125 at} −55 ° C. and + 125 ° C. based on the capacitance at 25 ° C. are −9.7%, 4 .3%, 2
0 ℃ capacitance -25 ° C. relative to the the, + 85 ° C. capacitance rate of change △ C _-25, △ C ₈₅ is -4.5%, - 2.6
%Met.

The electrical characteristics were measured at the following capacitances. (A) Relative permittivity ε_s Is a temperature of 20 ° C, a frequency of 1 kHz,
The capacitance was measured under the condition of a pressure (effective value) of 1.0 V.
The measured value and the facing area of the pair of internal electrodes 25 mm ^Two And one
Is the thickness of the dielectric porcelain layer between the pair of internal electrodes 0.015 mm
It was determined by calculation. (B) The dielectric loss tan δ (%) is the relative dielectric constant
The measurement was performed under the same conditions as in the measurement. (C) The resistivity ρ (MΩ · cm) is D at a temperature of 20 ° C.
After applying C100V for 60 seconds, between a pair of external electrodes
Is measured and calculated based on this measurement and dimensions
I asked for it. (D) Dielectric loss tan δ at AC voltage 200V / mm
(%) Is temperature 20 ° C, frequency 1kHz, voltage (execution
Value) Measured under the condition of 3.0 V. (E) The temperature characteristics of capacitance can be measured by placing a sample in a
55 ° C, -25 ° C, 0 ° C, + 20 ° C, + 25 ° C, +50
° C, + 85 ° C, + 110 ° C, + 125 ° C
At a frequency of 1 kHz and a voltage (effective value) of 1.0 V.
Measure the capacitance and measure the capacitance at 20 ° C and 25 ° C.
To find the rate of change of capacitance at each temperature with respect to capacitance
I got more.

As described above, the case of the sample No. 1 has been described. For the samples Nos. 2 to 89, the compositions of the basic components are changed as shown in Tables 3 to 3 and Tables 4 to 4, and Except that the composition and ratio were changed as shown in Tables 5 to 5, a laminated ceramic capacitor was prepared under exactly the same conditions as those of the sample of Sample No. 1, and the electrical characteristics were measured by the same method. The firing temperatures and the electrical characteristics of the samples Nos. 1 to 89 were as shown in Tables 6 to 6.

Tables 3 and 3 and Tables 4 and 4
2 shows the composition of the basic components of each sample and the ratio thereof. That is, x, y, and k are ratios of the number of atoms of each element in the composition formula (2) of the basic component described above, that is, Ti
The ratio of the number of atoms of each element is shown when the number of atoms in is 1. 1-z and z indicate the ratio of the number of atoms of each element of the composition formula (4) of the basic component described above. Α, β
Is the ratio of the number of atoms of each oxide in the composition formula (1) of the basic component described above, that is, the composition formula (1) of the basic component described above.
(1−γ) (Ba _{k− (x + y)} M _x L of the first, second and third terms in
_{y) O k TiO 2 + γ} ( showing the atomic ratio of the number of the oxides in the case of a 1 the number of molecules of _{R 1-z R 'z)} O 3/2.

Further, Mg and Zn in the column of x indicate the contents of M in the composition formula (1) of the above-mentioned basic component, and C and Zn in the column of y.
a and Sr indicate the contents of L in the composition formula (1) of the basic component, and La, Ce, Pr, Nd, Pm, and S in the column of 1-z.
m and Eu represent the contents of R in the composition formula (1) of the basic component described above, and Sc, Y, Gd, Tb, Dy, H in the column of z.
o, Er, Tm, Yb and Lu represent the contents of R ′ in the composition formula (1) of the basic component described above, and P and V in the column of α are:
The content of A in the composition formula (1) of the basic component described above is shown,
In the column of β, Cr, Mn, Fe, Co, and Ni indicate the contents of D in the composition formula (1) of the basic component described above.

Tables 5 to 5 show the composition of added components and their ratios for each sample.
The amount of the additional components in Tables 5 to 5 is 100
It is shown in parts by weight relative to parts by weight, and the MO
Are BaO, SrO, CaO, MgO and ZnO.
Are shown in mol%.

Tables 6 to 6 show firing temperatures and electrical characteristics of the laminated ceramic capacitors for each sample. In Tables 6 to 6, the temperature characteristics of the capacitance are expressed by the change rates of the capacitance at −55 ° C. and + 125 ° C. based on the capacitance at 25 ° C. as _{ΔC −55} (%) and ΔC _125. (%), The change rate of the capacitance at −25 ° C. and + 85 ° C. based on the capacitance at 20 ° C. is _{expressed as ΔC −25.}
(%) And ΔC ₈₅ (%).

[0060]

[Table 3]

[0061]

[Table 3]

[0062]

[Table 3]

[0063]

[Table 3]

[0064]

[Table 3]

[0065]

[Table 3]

[0066]

[Table 4]

[0067]

[Table 4]

[0068]

[Table 4]

[0069]

[Table 4]

[0070]

[Table 4]

[0071]

[Table 4]

[0072]

[Table 5]

[0073]

[Table 5]

[0074]

[Table 5]

[0075]

[Table 5]

[0076]

[Table 5]

[0077]

[Table 5]

[0078]

[Table 6]

[0079]

[Table 6]

[0080]

[Table 6]

[0081]

[Table 6]

[0082]

[Table 6]

[0083]

[Table 6]

As is apparent from the above results, according to the sample according to the present invention, 1200
By firing at a temperature of not more than ℃, the relative dielectric constant ε _{s of the} dielectric ceramic layer is 3
300 or more, tan δ is 2.5% or less, and resistivity ρ is 4.
0 × 10 ⁶ MΩ · cm or more, tan δ at an AC voltage of 200 V / mm is 3.0% or less, temperature change rates of capacitance _{ΔC −55} and ΔC ₁₂₅ are −15% to + 15%, ΔC ₋₂₅
And a porcelain capacitor having ΔC _{85 in} the range of −10% to + 10%.

On the other hand, sample numbers 2, 5, 6, 9, 1
0,13,23,28,29,31,32,34,3
8,39,44,45,49,62-67,74-78
And 83, a ceramic capacitor having desired electrical characteristics cannot be obtained. Therefore, the samples of these sample numbers are outside the scope of the present invention.

[0086] The temperature change rate of capacitance in Tables 6 _{6 △ C -55, △ C 125} , △ C -2 5, △ only the C ₈₅ is displayed, the samples according to the present invention -25 ° C to +
The temperature change rate ΔC of the capacitance in the range of 85 ° C. is −10%
To + 10%, and -55 ° C to +1
The temperature change rate ΔC of the capacitance in the range of 25 ° C. is −15%
It is within the range of + 15%.

Next, the reasons for limiting the composition range of the dielectric ceramic composition used in the ceramic capacitor according to the present invention are shown in Tables 3 to 3, Tables 4 to 4, and Tables 5 to 5.
This will be described with reference to the experimental results shown in Tables 6 to 6.

First, as shown in Sample Nos. 2 and 6, when α = 0.0002, the value of α was 200 V / AC voltage.
Although the tan δ in mm becomes 3.0% or more, as shown in Sample Nos. 3 and 7, when α = 0.0005, desired electrical characteristics can be obtained. Further, as shown in Sample No. 5 and 9, in the case of alpha = 0.011, the resistivity ρ is smaller than 4.0 × 10 ⁶ MΩ · cm, the temperature change rate of capacitance △ C _{-5 5} , ΔC ₁₂₅ is -15% to +1
△ C _-25 and △ C ₈₅ are -10% to +10
%, But as shown in sample numbers 4 and 8, α =
In the case of 0.01, desired electric characteristics can be obtained. Therefore, the range of α must be 0.0005 ≦ α ≦ 0.01.

The P and V of the A component work almost in the same way,
P and V in a range satisfying 0.0005 ≦ α ≦ 0.01
One or both can be used.

Next, as shown in Sample No. 10, when β = 0.0002, the value of β was 200 V / m AC voltage.
Although tan δ at m becomes 3.0% or more,
As shown in Sample No. 11, when β = 0.0005, desired electrical characteristics can be obtained. Sample No. 13
As shown in the figure, when β = 0.111, the relative dielectric constant is 3
However, when β = 0.01 as shown in Sample No. 12, desired electrical characteristics can be obtained. Therefore, the range of β is 0.0005 ≦ β ≦ 0.0
Must be 1.

It should be noted that D, Cr, Mn, Fe, Co,
Ni oxides work almost in the same way, and the same effect can be obtained by using one selected from these or by using a combination of two or more.

Next, as shown in Sample No. 39, when γ = 0, the temperature change rate ΔC- _{55 of the} capacitance deviates from -15% to + 15%, and the value of γ is 試_料 C- _25. -10% to +
Although it deviates from 10%, as shown in Sample No. 40, when γ = 0.002, desired electrical characteristics can be obtained. Further, as shown in sample number 44, γ = 0.0
In the case of No. 7, a dense sintered body having desired electrical characteristics cannot be obtained, but as shown in Sample No. 43, γ = 0.
In the case of 06, desired electrical characteristics can be obtained. Therefore, the range of γ must be 0.002 ≦ γ ≦ 0.06.

Next, as shown in Sample No. 23, when x + y = 0, the temperature change rate ΔC- _{55 of the} capacitance deviates from −15% to + 15% as shown in Sample No. 23. As shown in numbers 24 and 25, when x + y = 0.01, desired electrical characteristics can be obtained. Sample No. 29, 3
As shown in FIG. 1, when x + y = 0.11, the temperature change rate ΔC _{85 of the} capacitance deviates from −10% to + 10%, but as shown in Sample No. 33, x + y = 0. .
In the case of 10, desired electrical characteristics can be obtained. However,
As shown in Sample Nos. 28 and 32, even when x + y ≦ 0.10, when the value of y exceeds 0.05, the temperature change rate ΔC _{85 of the} capacitance deviates from −10% to + 10%. I will. Therefore, the range of x + y is 0.01 ≦ x + y ≦ 0.
10, but at the same time y ≦ 0.05.

Incidentally, Mg and Zn of the M component and C and C of the L component
a and Sr work almost in the same way, and use one or both of Mg and Zn in a range satisfying 0 ≦ x ≦ 0.10, and use Ca and S in a range satisfying 0 ≦ y ≦ 0.05. One or both of Sr can be used. However, in any case of one or more of the M component and the L component, the value of x + y must be in the range of 0.01 to 0.10.

Next, as shown in Sample No. 34, when k <1.00, the resistivity ρ is 4.0 × 10
⁶ MΩ · cm, the capacitance temperature change rates ΔC ₋₅₅ and ΔC ₁₂₅ deviate from −15% to + 15%, and ΔC ₋₂₅ and ΔC _{85 change} from −10% to + 10%. However, as shown in Sample No. 35, k = 1.00
In this case, desired electrical characteristics can be obtained. On the other hand, when the value of k is k> 1.05 as shown in Sample No. 38, a dense sintered body cannot be obtained, but as shown in Sample No. 37, k = 1.05. In this case, desired electrical characteristics can be obtained. Therefore, the range of k is 1.00
≦ k ≦ 1.05.

Next, as shown in Sample No. 45, when z = 0.4, tan δ becomes 2.5% or more, and tan δ at an AC voltage of 200 V / mm is 3.
0% or more and the resistivity ρ is 4.0 × 10 ⁶ MΩ · cm
And the temperature change rate of capacitance _温度 C _-55 , △ C
₁₂₅ deviates from -15% to + 15%, ΔC _-25 , ΔC
_{Although 85} deviates from -10% to + 10%, as shown in Sample No. 46, when z = 0.5, desired electrical characteristics are obtained. Also, as shown in sample number 49,
In the case of z = 0.95, the relative dielectric constant becomes 3300 or less.
In this case, desired electrical characteristics can be obtained. Therefore, z
Range is 0.5 ≦ z ≦ 0.9.

Note that the R components La, Ce, Pr, Nd,
Pm, Sm and Eu, Sc, Y, Gd, T of R ′ component
b, Dy, Ho, Er, Tm, Yb and Lu work almost in the same way, and the same effect can be obtained by using one selected from these or by using a combination of two or more. is there.

Next, a preferable range of the additive component will be examined. First, when the additive component is Li ₂ O—SiO ₂ —MO, the preferred composition range of the additive component is Li ₂ O—Si
The composition ratio of O ₂ -MO can be determined based on the triangular diagram of FIG.

The first point A in this triangular diagram (FIG. 2)
Means that as shown in Sample No. 52, Li ₂ O is 1 mol%,
SiO ₂ is 80 mol%, MO indicates the composition of 19 mol%, B second point, as shown in Sample No. 53, Li ₂
O has a composition of 1 mol%, SiO ₂ has 39 mol%, and MO has 60 mol%. The third point C indicates that as shown in sample No. 54, 30 mol% of Li ₂ O and 30 mol% of SiO ₂ Mole%,
MO shows a composition of 40 mol%, and a fourth point D shows that, as shown in sample No. 55, 50 mol% of Li ₂ O and SiO ₂
Has a composition of 50 mol% and MO of 0 mol%. The fifth point E is, as shown in sample No. 56, that 20 mol% of Li ₂ O, 80 mol% of SiO _{2 and} 0 mol% of MO Is shown.

As shown in Sample Nos. 52 to 61, the composition range of the additive component is represented by the first to fifth points in a triangular diagram (FIG. 2) in which the composition ratio of Li ₂ O—SiO ₂ —MO is represented by mol%. AE
The desired electrical characteristics can be obtained within a range surrounded by five straight lines connecting
As shown in the above, if the composition of the additive component is out of the above range, a dense sintered body cannot be obtained.

Next, the additive component is B ₂ O ₃ —SiO ₂ —M
In the case of O, a preferable composition range of the additional component is B ₂ O ₃ −
The composition ratio of SiO ₂ -MO can be determined based on the triangular diagram of FIG.

The sixth point F in this triangular diagram (FIG. 3)
Means that as shown in sample No. 68, B ₂ O ₃ is 1 mol%,
SiO ₂ is 80 mol%, MO indicates the composition of 19 mol%, G seventh point, as shown in Sample No. 69, B ₂ O
₃ is 1 mol%, SiO ₂ is 39 mol%, MO is 60 mol%, and the eighth point H is, as shown in sample No. 70, B ₂ O ₃ is 29 mol% and SiO ₂ is 1 mol%, M
O indicates a composition of 70 mol%, and a ninth point I indicates a composition of 90 mol% of B ₂ O _3, 1 mol% of SiO _{2 and} 9 mol% of MO as shown in sample No. 71. , The tenth point J
Indicates a composition of 90 mol% of B ₂ O ₃ , 9 mol% of SiO ₂ , and 1 mol% of MO as shown in Sample No. 72. The eleventh point K is as shown in Sample No. 73. And B ₂
It has a composition in which O ₃ is 19 mol%, SiO ₂ is 80 mol%, and MO is 1 mol%.

As shown in Sample Nos. 68 to 73, the composition range of the added component is sixth to eleventh in a triangular diagram (FIG. 3) in which the composition ratio of B ₂ O ₃ —SiO ₂ —MO is represented by mol%. Point F ~
Although desired electrical characteristics can be obtained within a range surrounded by six straight lines connecting K in order, sample numbers 74 to 7 can be obtained.
As shown in 7, if the composition of the additive component is out of the above range, a dense sintered body cannot be obtained.

The components of MO were as shown in sample numbers 84 to 88.
As shown in BaO, SrO, CaO, MgO,
Any one of ZnO may be used, or an appropriate ratio of two or more may be used as shown in other samples.

Next, as shown in Sample No. 78, when the addition amount is 0 parts by weight, even if the firing temperature is 1250 ° C., the value of the addition amount of the Is not obtained, but as shown in Sample No. 79, when the addition amount is 0.2 parts by weight with respect to 100 parts by weight of the basic component, 11
Desired electrical characteristics are obtained at a firing temperature of 90 ° C. On the other hand, as shown in sample number 83,
In the case of 7.0 parts by weight in terms of 100 parts by weight of the basic component, the relative dielectric constant becomes less than 3300, and the temperature change rate ΔC- _{55 of the} capacitance deviates from −15% to + 15%. As shown in Sample No. 82, the amount of the additive
When the amount is 5.0 parts by weight with respect to 100 parts by weight of the basic component, desired electric characteristics can be obtained. Therefore, the added amount of the additive component is 0.1 to 100 parts by weight of the basic component.
It is in the range of 2 to 5.0 parts by weight.

In the above description, as an additive component,
Li ₂ O-SiO ₂ -MO or B ₂ O ₃ -SiO ₂ -M
Although O is used alone, as shown in Sample No. 89,
When the content is in the range of 0.2 to 5.0 parts by weight with respect to 100 parts by weight of the basic component, the same effect is exhibited even when these two types of additive components are used in combination.

[0107]

According to the present invention, the relative dielectric constant ε _{s of the} dielectric ceramic layer is 3300 or more, the dielectric loss tan δ is 2.5% or less, the resistivity ρ is 4.0 × 10 ⁶ MΩ · cm or more, Dielectric loss tan δ at an AC voltage of 200 V / mm is 3.0%
And the temperature change rate of the capacitance is −55 ° C.
-15% to + 15% at 125 ° C (based on 25 ° C), -2
There is an effect that a porcelain capacitor falling within a range of -10% to + 10% (based on 20 ° C) at 5 ° C to 85 ° C can be provided.

In particular, according to the present invention, an AC voltage of 200 V
Since the dielectric loss tan δ at / mm is as good as 3.0% or less, an increase in the dielectric loss when the dielectric ceramic layer is thinned can be suppressed, and therefore a small and large-capacity ceramic capacitor can be provided. There is an effect that can be.

Further, according to the present invention, since the dielectric ceramic composition constituting the dielectric layer of the ceramic capacitor is formed by firing in a non-oxidizing atmosphere, the internal electrodes are made of inexpensive base metal such as nickel. It can be formed of a conductive paste, and thus has an effect that an inexpensive porcelain capacitor can be provided.

[Brief description of the drawings]

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

FIG. 2 shows the additive component (Li ₂ O—SiO ₂ ) of the dielectric ceramic composition constituting the dielectric layer of the ceramic capacitor according to the present invention.
FIG. 3 is a triangular diagram showing a composition range of (−MO).

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

[Explanation of symbols]

 Reference Signs List 12 dielectric ceramic layer 14 internal electrode 15 laminated sintered 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]

[Table 6 ○ 1]

[Table 6 ○ 2]

[Table 6 ○ 3]

[Table 6 ○ 4]

[Table 6 ○ 5]

[Table 6 ○ 6]

Continuation of the front page (72) Inventor Hiroshi Kishi 6-16-20 Ueno, Taito-ku, Tokyo Taiyo Yuden Co., Ltd. (56) References JP-A-5-282918 (JP, A) JP-A-5-282917 ( JP, A) JP-A-3-174710 (JP, A) JP-A-3-177010 (JP, A) JP-A-3-133116 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , (DB name) H01G 4/12

Claims (4)

(57) [Claims] 1. A ceramic capacitor comprising one or more dielectric ceramic layers made of a dielectric ceramic composition, and at least two or more internal electrodes sandwiching the dielectric ceramic layer, wherein: The porcelain composition comprises a mixture obtained by calcining a mixture of 100.0 parts by weight of a basic component and 0.2 to 5.0 parts by weight of an additional component, wherein the basic component is (1−γ) (Ba _{k -(x + y)} M _x L _y ) O _k TiO ₂ + γ (R
_1-z R ′ _z ) O _3/2 + αAO _5/2 + βD (where M is Mg and / or Zn, L is Ca and / or Sr, R is La, Ce, P
one or more elements selected from r, Nd, Pm, Sm and Eu, and R 'is Sc, Y, Gd, Tb, Dy,
One or more elements selected from Ho, Er, Tm, Yb and Lu, A is P and / or V, D is Cr, M
One or more oxides selected from n, Fe, Co and Ni, α, β, γ, k, x, y and z are 0.0005 ≦ α ≦ 0.01 0.0005 ≦ β ≦ 0.01 0.002 ≦ γ ≦ 0.06 1.00 ≦ k ≦ 1.05 0 ≦ x <0.10 0 ≦ y ≦ 0.05 0.01 ≦ x + y ≦ 0.10 0.5 ≦ z ≦ 0.9), wherein the additional components are Li ₂ O, SiO ₂ and MO (where MO
Is one or more oxides selected from BaO, SrO, CaO, MgO, and ZnO), and the composition range of the Li ₂ O, the SiO _2, and the MO is % In the triangular diagram, 1 mol% of Li ₂ O, 80 mol% of SiO ₂ ,
A first point A where the MO has a composition of 19 mol%, 1 mol% of the Li ₂ O, 39 mol% of the SiO ₂ ,
A second point B indicating a composition of the MO of 60 mol%, and a third point C indicating a composition of the Li ₂ O of 30 mol%, the SiO ₂ of 30 mol%, and the MO of 40 mol%. A fourth point D indicating 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 %, Said MO being in a region surrounded by five straight lines connecting in this order a fifth point E indicating a composition of 0 mol%. 2. A ceramic capacitor comprising one or two or more dielectric ceramic layers made of a dielectric ceramic composition and at least two or more internal electrodes sandwiching the dielectric ceramic layers, The porcelain composition comprises a material obtained by calcining a mixture of 100.0 parts by weight of a basic component and 0.2 to 5.0 parts by weight of an additional component, and a material represented by the following numerical value: The basic component is (1−γ) (Ba _{k− (x + y)} M _x L _y ) O _k TiO ₂ + γ (R
_1-z R ′ _z ) O _3/2 + αAO _5/2 + βD (where M is Mg and / or Zn, L is Ca and / or Sr, R is La, Ce, P
one or more elements selected from r, Nd, Pm, Sm and Eu, and R 'is Sc, Y, Gd, Tb, Dy,
One or more elements selected from Ho, Er, Tm, Yb and Lu, A is P and / or V, D is Cr, M
one or more oxides selected from n, Fe, Co and Ni, α, β, γ, k, x, y and z are 0.0005 ≦ α ≦ 0.01 0.0005 ≦ β ≦ 0.01 0.002 ≦ γ ≦ 0.06 1.00 ≦ k ≦ 1.05 0 ≦ x <0.10 0 ≦ y ≦ 0.05 0.01 ≦ x + y ≦ 0.10 0.5 ≦ z ≦ 0.9 The additional components are B ₂ O ₃ , SiO ₂ and MO (where MO
Is one or more oxides selected from BaO, SrO, CaO, MgO and ZnO), and the composition range of the B ₂ O ₃ , the SiO ₂ and the MO is in a triangular diagram showing a mole%, the B ₂ O ₃ 0 is 1 mol%, the SiO ₂ is 80 mol%, and the sixth point F indicating the composition of the MO is 19 mol%, the B ₂ O ₃ 1 mol%, 39 mol% of the SiO ₂ ,
A seventh point G indicating a composition in which the MO is 60 mol%, 29 mol% of the B ₂ O ₃ , 1 mol% of the SiO ₂ ,
An eighth point H indicating a composition in which the MO is 70 mol%, the B ₂ O ₃ is 90 mol%, the SiO ₂ is 1 mol%,
A ninth point I indicating a composition in which the MO is 9 mol%, the B ₂ O ₃ is 90 mol%, the SiO ₂ is 9 mol%,
A tenth point J indicating the composition of the MO of 1 mol%, and an eleventh point J indicating the composition of the B ₂ O ₃ of 19 mol%, the SiO ₂ of 80 mol%, and the MO of 1 mol% A ceramic capacitor which is located in a region surrounded by six straight lines connecting K in this order. 3. A step of preparing a mixture comprising unsintered porcelain powder; a step of forming a non-sintered porcelain sheet comprising the mixture; and a step of forming the unsintered porcelain sheet into at least two or more conductive paste films. Forming a laminate sandwiched by the above, 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 porcelain composition comprises a material obtained by calcining a mixture of 100.0 parts by weight of a basic component and 0.2 to 5.0 parts by weight of an additional component, and a material represented by the following numerical value: The basic component is (1−γ) (Ba _{k− (x + y)} M _x L _y ) O _k TiO ₂ + γ (R
_1-z R ′ _z ) O _3/2 + αAO _5/2 + βD (where M is Mg and / or Zn, L is Ca and / or Sr, R is La, Ce, P
one or more elements selected from r, Nd, Pm, Sm and Eu; R ′ is Sc, Y, Gd, Tb, Dy,
One or more elements selected from Ho, Er, Tm, Yb and Lu, A is P and / or V, D is Cr, M
One or more oxides selected from n, Fe, Co and Ni, α, β, γ, k, x, y and z are 0.0005 ≦ α ≦ 0.01 0.0005 ≦ β ≦ 0.01 0.002 ≦ γ ≦ 0.06 1.00 ≦ k ≦ 1.05 0 ≦ x <0.10 0 ≦ y ≦ 0.05 0.01 ≦ x + y ≦ 0.10 0.5 ≦ z ≦ 0.9 The additive component is Li ₂ O, SiO ₂ and MO (however, MO
Is one or more oxides selected from BaO, SrO, CaO, MgO, and ZnO), and the composition range of the Li ₂ O, the SiO _2, and the MO is % In the triangular diagram, 1 mol% of Li ₂ O, 80 mol% of SiO ₂ ,
A first point A where the MO has a composition of 19 mol%, 1 mol% of the Li ₂ O, 39 mol% of the SiO ₂ ,
A second point B indicating a composition of the MO of 60 mol%, and a third point C indicating a composition of the Li ₂ O of 30 mol%, the SiO ₂ of 30 mol%, and the MO of 40 mol%. A fourth point D indicating 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 %, Wherein said MO is in a region surrounded by five straight lines connecting in this order a fifth point E indicating a composition of 0 mol%. 4. A step of preparing a mixture comprising unsintered porcelain powder, a step of forming a non-sintered porcelain sheet comprising the mixture, and forming the unsintered porcelain sheet into at least two or more conductive paste films. Forming a laminate sandwiched by the above, 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 porcelain composition comprises a material obtained by calcining a mixture of 100.0 parts by weight of a basic component and 0.2 to 5.0 parts by weight of an additional component, and a material represented by the following numerical value: The basic component is (1−γ) (Ba _{k− (x + y)} M _x L _y ) O _k TiO ₂ + γ (R
_1-z R ′ _z ) O _3/2 + αAO _5/2 + βD (where M is Mg and / or Zn, L is Ca and / or Sr, R is La, Ce, P
one or more elements selected from r, Nd, Pm, Sm and Eu, and R 'is Sc, Y, Gd, Tb, Dy,
One or more elements selected from Ho, Er, Tm, Yb and Lu, A is P and / or V, D is Cr, M
One or more oxides selected from n, Fe, Co and Ni, α, β, γ, k, x, y and z are 0.0005 ≦ α ≦ 0.01 0.0005 ≦ β ≦ 0.01 0.002 ≦ γ ≦ 0.06 1.00 ≦ k ≦ 1.05 0 ≦ x <0.10 0 ≦ y ≦ 0.05 0.01 ≦ x + y ≦ 0.10 0.5 ≦ z ≦ 0.9 The additional components are B ₂ O ₃ , SiO ₂ and MO (where MO
Is one or more oxides selected from BaO, SrO, CaO, MgO and ZnO), and the composition range of the B ₂ O ₃ , the SiO ₂ and the MO is in a triangular diagram showing a mole%, the B ₂ O ₃ 0 is 1 mol%, the SiO ₂ is 80 mol%, and the sixth point F indicating the composition of the MO is 19 mol%, the B ₂ O ₃ 1 mol%, 39 mol% of the SiO ₂ ,
A seventh point G indicating a composition in which the MO is 60 mol%, 29 mol% of the B ₂ O ₃ , 1 mol% of the SiO ₂ ,
An eighth point H indicating a composition in which the MO is 70 mol%, the B ₂ O ₃ is 90 mol%, the SiO ₂ is 1 mol%,
A ninth point I indicating a composition in which the MO is 9 mol%, the B ₂ O ₃ is 90 mol%, the SiO ₂ is 9 mol%,
A tenth point J indicating the composition of the MO of 1 mol%, and an eleventh point J indicating the composition of the B ₂ O ₃ of 19 mol%, the SiO ₂ of 80 mol%, and the MO of 1 mol% A method for producing a ceramic capacitor, wherein the method is in a region surrounded by six straight lines connecting K in this order.