JPH03171711A - Porcelain capacitor and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain dielectric porcelain having high permittivity and a low rate of temperature change of permittivity over a wide temperature range by making Ba, Mg, Zn, Ti, etc., a fundamental component and adding an additive component such as Li, Si, etc., to it at a particular ratio. CONSTITUTION:A pair of external electrodes 16 are attached to a laminated sintered chip 15 consisting of three dielectric porcelain layers 12 and two internal electrodes 14 to form a laminated porcelain capacitor 10. The main component of this dielectric porcelain layer consists of (1-alpha){(Bak-xMx)Ok(Ti1-yRy) O2-y/2}+alphaCaZrO3 (where M is at least one of metal selected from between Mg, Zn, and R is at least one kind of metal from among Sc, Y, Gd, Dy, Ho, Er, Yb, Tb, Tm, Lu), and an additive component consists of at least one of metal oxide from among Li2O, SiO2 and MO (where MO is at least one of metal oxide from among BaO, SrO, CaO, MgO and ZnO). The relative permittivity of this dielectric porcelain is not less than 3000, and the rate of temperature change of the relative permittivity thereof is -15%-+15% at -55 deg.C-125 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a ceramic capacitor having a single-layer or laminated structure made of dielectric ceramic and at least two electrodes, and a method for manufacturing the same. [Prior Art] Conventionally, when manufacturing multilayer ceramic capacitors, a desired pattern of conductive paste of a precious metal such as platinum or palladium is applied to a green sheet (unsintered porcelain sheet) made of dielectric porcelain raw material powder. The sheets were printed on paper, stacked and pressed together, and sintered in an oxidizing atmosphere at 1,300°C to 1,600°C. This allows the dielectric ceramic and internal electrode to be obtained at the same time. As mentioned above, if noble metals are used, the desired internal electrodes can be obtained even if sintered at high temperatures in an oxidizing atmosphere. However, because precious metals such as platinum and palladium are expensive, the cost of multilayer ceramic capacitors has inevitably increased. As a solution to the above-mentioned problem, Japanese Patent Publication No. 14607/1987, filed by the applicant, describes a method consisting of (Bak-xMx)OkTIO2 (where M is at least one of Mg and Zn). Basic ingredients and L
A dielectric ceramic composition containing an additive component 2 consisting of i O and S i O 2 is disclosed. In addition, the above-mentioned Japanese Patent Publication No. 14608/1983 includes the above-mentioned
Instead of L 1 2 0 and S i O 2 in Publication No. 14607, Li20, SiO2 and MO (however, MO is Ba
A dielectric ceramic composition is disclosed that includes an additive component consisting of at least #JIM> of O, CaO, and SrO.

Moreover, in Japanese Patent Publication No. 61-14609, (Ba1<
-x-y MxLy) OkTtO2 (However, M is Mg
and at least one of Zn, L is at least one of Sr and Ca), Li O and S I
A 2 dielectric porcelain composite containing an additive component consisting of O 2 is disclosed. In addition, Japanese Patent Publication No. 61-14610 also includes 120 and 8102 in the above-mentioned Japanese Patent Publication No. 61-14609.
Instead, a dielectric ceramic composition containing additive components consisting of L i 2 0, S i O 2, and MO (where MO is at least one of BaO, CaO, and SrO) is disclosed. In addition, in Japanese Patent Publication No. 14611/1983, (B a
M ) O T i 02 (However, M
g, k-xxk Zn. A dielectric ceramic composition is disclosed that includes a basic component consisting of at least one of Sr and Ca) and an additional component consisting of B O and SiO2.

In addition, in Japanese Patent Publication No. 1595/1983, <Ba
M) O T 1 02 (f day, M is M
g, Zk-xxk n, Sr and Ca), B203 and MO (however, MO is BaO, MgO,
A dielectric ceramic composition containing at least one of ZnO, SrO, and CaO) and a certain additive component is disclosed. In addition, in Japanese Patent Publication No. 62-1596, instead of B2o3 and MO in the above-mentioned Japanese Patent Publication No. 62-1595,
3 1 0 2 and an additive component consisting of MO (where MO23 is at least one of BaO, MgO, ZnO.SrO, and CaO) is disclosed. The invitations disclosed in these @
．． The body porcelain composition can be obtained by firing in a reducing atmosphere at 1200°C or lower, has a dielectric constant of 2000 or more, and has a temperature change rate of capacitance in the range of ±10% from -25°C to +85°C. It is something that can be done. [The problem that the invention tries to solve! ] By the way, with the recent increase in the density of electronic circuits, there is a strong demand for miniaturization of multilayer capacitors. It is desired to further increase the relative dielectric constant of the dielectric ceramic composition disclosed in each publication. Therefore, the purpose of the present invention is to use a non-oxidizing atmosphere at 1200°C.
A ceramic capacitor comprising dielectric ceramic that has a high dielectric constant and a small temperature change rate of dielectric constant over a wide temperature range, even though it is obtained by firing at the following temperatures, and a method for manufacturing the same: Our goal is to provide the following.

[Means for Solving the Problems] To achieve the above object, the present invention provides a ceramic capacitor comprising a dielectric ceramic and at least two electrodes in contact with the ceramic, wherein the ceramic is 100. It consists of 0 parts by weight of basic components and 0.2 to 5.0 parts by weight of additional components, and the basic precepts are (1-α)((Ba M
)O (Ti Rk-XXk 1-y )O l +αCaZr03 (However, M is at least one metal among V 2-y/2 Mg, Zn, R is Sc, Y
, Gd. ．． Dy, Ho, Er, Yb, Tb, Tm. Lu
at least one metal of the following, α is 0.005 to 0.0
4, k is a value in the range of 1.00 to 1.05, X is a value in the range of 0.0i to 0.10, y is 0.0
4 or less), and the additive components are L i 2 0, StO2, and MO<However, MO is BaO
, SrO, CaO, MgO and ZnO), and the L l 2 0
The composition range of the SiO2 and the MO is such that the L l 2 0 in the triangular diagram showing these compositions in mol% is 1.
Point (A) where the S I O 2 is 80 mol % and the MO is 19 mol %, and the point (A) where the L i 2 0 is 1 mol %, the S I O 2 is 39 mol %, and the MO is 60 mol %
Point (B) of mol%, the Li20' is 30 mol%, the S102 is 30 mol%, and the MO is 40 mol%.
point (C), the point (D) where the L l 2 0 is 50 mol %, the S 1 0 2 is 50 mol %, the MO is O mol %, the L l 2 0 is 20 mol %, The Si
This relates to a capacitor that is within an area surrounded by five straight lines connecting in order the point (E) where O2 is 80 mol % and MO is 0 mol %. In addition, in the composition formula showing the basic components, ゜[, k-x, x. k, 1-y, y, 2-y/
2 of course indicates the number of atoms of each element, and (1-α) and α are (Ba(-xMx)Ok(Ti1, , 2-,
72 and the second term CaZr03 in moles, Ba is barium, 0 is oxygen, Ti is titanium, M
g is magnesium and Zn is zinc. In addition, Sc is scandium, Y is yttrium, Gd is gadolinium,
Dy is dysprosium, HO is holonium, Er is erbium, Yb is ytterbium, Tb is terbium, T
m is thulium and Lu is lutetium. In the additive precepts, Li20 is lithium oxide, S 1 0 2 is silicon oxide, BaO is barium oxide, SrO is strontium oxide, CaO is calcium oxide, MgO is magnesium oxide, and ZnO is zinc oxide. The invention related to the manufacturing method includes a step of preparing a mixture of the above-mentioned basic component and an additive component, and at least two steps! a step of producing a molded article of the mixture having an electrode portion; a step of firing the molded article having the electrode portion in a non-oxidizing atmosphere; and a step of heat-treating the molded article obtained by the firing in an oxidizing atmosphere. This relates to the manufacturing method of porcelain capacitors, including porcelain capacitors. [Operations and Effects] The dielectric ceramic in the ceramic capacitor of the above invention can be obtained by firing in a non-oxidizing atmosphere at 1200°C or lower.
Therefore, it becomes possible to manufacture a ceramic capacitor by applying a conductive paste of a base metal such as nickel to a green sheet and firing the green sheet and the conductive paste simultaneously. By setting the composition of the dielectric ceramic within the range specified in the present invention, the dielectric constant is 3000 or more, the dielectric loss tan δ is 2.5% or less, and the resistivity ρ is I.
X106MΩ・cm or more, and the temperature change rate of relative dielectric constant is -15% to +15% (25
(based on ℃), -10% to +10% at -25℃ to 85℃
(Reference: 20°C) It is possible to provide a capacitor equipped with porcelain. [Example A] Next, examples and comparative examples according to the present invention will be described. First, according to the present invention Compositional formula of basic components (1 −α 冫 ((Ba k−x M x
)O k (Ti 1, R)O )+
(Ba M ) O (Ti R ) Ok- of the first term Y 2-y/2 in αCaZrO3
x x k 1-y y 2-y/
2 (hereinafter referred to as the first basic component) at the ratio shown in the k-x, x, y, k column of sample No. 1 in Tables 1 and 2, in other words, (Ba0.96M0. 06)0
(TiR)O, more specifically 1.0
2 0.99 0.01 1.99
5! Yo- MO. 06=MgO. 05ZnO. 01 and Ro. ot= Y bo. Since oi, (Ba0.96Mgo.asZnQ.01) 01.
02'T' 0.99YbO. 01) To obtain 01.995, B a C O 3 with a purity of 99.0% or more
(barium carbonate), MgO (magnesium oxide), Zn
O (zinc oxide), and Tie (titanium oxide), Yb20
3 (ytterbium oxide), without adding any impurities, BaCO: 1041.96g (equivalent to 0.96 mol 3 parts) MgO: 1 1.09g (equivalent to 0.05 mol part) Z
nO: 4.48g (equivalent to 0.01 mole part) TiO2
: 435.06 g (equivalent to 0.99 mol part) Yb O : 10.84 g (equivalent to 0.005 mol part 23) were weighed. Next, these weighed raw materials are put into a bot mill (pot mill).
Add alumina ball and 2.5j of water.
After wet stirring for 15 hours, the stirred material was placed in a stainless steel pot and dried in a hot air dryer at 150°C for 4 hours. Next, this dried material was coarsely pulverized, and the coarsely pulverized material was calcined in the atmosphere at 1200° C. for 2 hours in a tunnel furnace to obtain the first basic precept of the above compositional formula. In addition, in order to obtain CaZrO3 (hereinafter referred to as the second basic component) in the second term of the compositional formula of the basic component, CaCO
(Calcium carbonate) and Z r O 2 (3 zirconium oxide) were added to 448.9 mols of the former so that they were equal in mole.
6g of the latter and 551.04g of each were weighed, mixed, dried, crushed, and then calcined in the air at about 1250°C for 2 hours. Next, as shown in sample Nα1 in Table 1, 98 mol parts (984.34 g) of the first basic component (Ba0.96MgO .05ZnO.01)01.0
2 (T'0.99"b0.01>01.995 powder and 2 mole parts (15.66 g) of the second basic component (
C a Z r O s ) powder and mixed with 100
0g of basic ingredients were obtained. On the other hand, in order to obtain the additive amount of sample Nα1 in Table 3, 0.44 g of L i 2 0 (
1 mole part), 70.99 g (80 mole parts) of SiO2, and 11.9 g (80 mole parts) of Baco3. Log (3.8 mole parts)
Weighed 14.70 g (9.5 mol parts) of Caco3 and 3.40 g (5.7 mol parts) of MgO, added 300 cc of alcohol to this mixture, and made alumina balls in a polyethylene bottle. After stirring for 10 hours, the mixture was calcined in the air at 1000°C for 2 hours, placed in an alumina pot with 300cc of water, crushed with an alumina ball for 15 hours, and then dried at 150°C for 4 hours. L 1 2 0 is 1 mol %, S 1 0
2 is 80 mol%, MO is 19 mol% (BaO 3.8
A powder of additive components having a composition of 9.5% monomer + 9.5 mol% Ca + 5.7 mol% MgO was obtained. Note that the proportions of BaO, CaO, and MgO, which are the contents of MO, are 20 mol%, 50 mol%, and 30 mol%, as shown in Table 3.
Next, 100fJ. 2 for the basic precepts of quantity (1000g)
Parts by weight (20 g) of additives were added, and an organic binder consisting of an aqueous solution of acrylic acid ester polymer, glycerin, and condensed phosphate was added in an amount of 15% by weight based on the total weight of the basic components and additive components. Then, 50% by weight of water was added, and these were placed in a ball mill to be ground and mixed to prepare a slurry of porcelain raw materials. Next, the above slurry is put into a vacuum deaerator to defoam 2, and this slurry is put into a reverse roll coater, and the thin film molded product obtained therefrom is continuously received on a long polyester film, and the same Heat this on the film at 100℃
The material was heated to dry to obtain an unsintered porcelain sheet with a thickness of about 25 μm. This sheet is long, but it is
01 Cut into squares and use. On the other hand, the conductive paste for the internal $ electrode has an average particle size of 1.5μ
10g of nickel powder and 0.9g of ethyl cellulose
was dissolved in 9.1 g of butyl carbitol, then placed in a stirrer and stirred for 10 hours. This conductive paste was printed on one side of the unsintered porcelain sheet through a screen having 50 patterns 14 in length and 7 in width, and then dried. Next, two unsintered porcelain sheets were laminated with the printed side facing up. At this time, the adjacent upper and lower sheets were arranged so that their printed surfaces were shifted by about half in the longitudinal direction of the pattern. Furthermore, 8 sheets of unsintered porcelain with a thickness of 60 μm were placed on each of the top and bottom surfaces of this laminate. Layered. Next, this laminate was compressed at a temperature of about 50° C. by applying a load of about 40 tons in the thickness direction. Thereafter, this laminate was cut into a grid shape to obtain 50 laminate chips. Next, this laminate was placed in a furnace capable of firing in an atmosphere, and the temperature was raised to 600°C at a rate of 100°C/h in an air atmosphere to burn the organic binder. Thereafter, the atmosphere in the furnace was changed from air to an atmosphere containing H2 (2% by volume) and N2 (98% by volume). Then, while maintaining the reducing atmosphere in the furnace as described above, the laminate ripening temperature was increased from 600°C to the sintering temperature of 1150°C at a rate of 100°C/h.
After holding 50℃ (maximum temperature) for 3 hours, 100℃/
The temperature is lowered to 600℃ at a rate of h, and the atmosphere is changed to an atmospheric atmosphere (
The sample was changed to an oxidizing atmosphere (oxidizing atmosphere), maintained at 600°C for 30 minutes, and then subjected to oxidation treatment, and then cooled to room temperature to produce a WI layer sintered chip. Next, in order to obtain the M-layer ceramic capacitor 10 shown in FIG.
A laminated sintered chip 15 consisting of
A pair of external electrodes 16 were installed. Note that the external electrode 16
Zinc, glass frit (gfass frit) and vehicle (
A conductive paste consisting of a vehicle) is applied and dried, and this is baked in the air at a temperature of 550° C. for 15 minutes to form a zinc electrode layer 18, and a copper layer 20 is further applied on this by electroless plating. A pb-Sn solder layer 22 is formed on the pb-sn solder layer 22 by electroplating. The thickness of the dielectric ceramic layer 12 of this capacitor 10 is 0.02 m,
The opposing area of the pair of internal electrodes 14 is 5 wmX 5 am
= 2 5 ma 2. Nao, fi m f&
of? The composition of the third layer 12 is substantially the same as the mixture of the basic components and some additives before sintering. Next, the electrical characteristics of the capacitor 10 were measured and the average values were calculated. As shown in Table 3, the relative dielectric constant ε3 was 3930, the tan δ was 1.1%, and the resistivity ρ was 6.5
06MΩ・CI1, -5 based on capacitance at 25℃
Rate of change of capacitance ΔC, ΔC at 5℃ and +125℃
125 is -10.2%, -55 +3.1%, -25℃ based on the capacitance at 20℃,
The capacitance change rates ΔC- and Δ25C85 at +85°C were -5, 5%, and -6.0%. The electrical characteristics were measured as follows. (A) Relative permittivity ε,
is a temperature of 20°C, a frequency of 1 kHz, and a voltage (effective value) of 1
．． The capacitance was measured under OV conditions, and the measured value was calculated from the opposing area of the pair of internal electrodes 14 (25cm2) and the thickness of the ceramic layer 12 between the pair of internal electrodes 14 (0.02+m+).
(B) Dielectric loss tanδ (%) was measured under the same conditions as the relative dielectric constant. (C) Resistivity ρ《MΩ・cIm) is determined by measuring the resistance value between a pair of external t-poles 16 after applying DC 100V for 1 minute at a temperature of 20°C, and based on this measured value and dimensions. Obtained by calculation. (D) Temperature characteristics of capacitance were determined by placing the sample in a constant temperature bath, -55°C, -25°C, 0°C, +20°C, 25°C,
+40℃, +60℃, +85℃, +105℃, +125
At each temperature in °C, the frequency l kHz. Voltage (effective value) 1. The capacitance was measured under OV conditions, 20'C and 2
It was obtained by calculating the rate of change at each temperature with respect to the capacitance at 5°C. The preparation method of sample Nα1 and its characteristics have been described above, but for samples NQ2 to 131, the compositions of basic components and added components, their proportions, and the firing temperature in a reducing atmosphere are shown in Table 1. A Wi-layer ceramic capacitor was manufactured in exactly the same manner as Sample Nα1, except for the changes shown in Table 4, and its electrical characteristics were measured in the same manner. Table 1 shows (1-α) in the composition formula showing the basic precepts.
and α2)k-x and shows the total value (X value) of these. Table 2 shows the content and amount of R and the value of k in the composition formula showing the basic components. That is, Se in the y column , Y, ' Gd, DV, Ho, Er, Yb indicate the content of R in the general formula, the number of atoms of these is shown in these columns, and the total value of these is shown in the total column. , : indicates the added amount of the added ingredient for each sample.The added amount of the added ingredient is shown in parts by weight based on 100 parts by weight of the basic ingredient. In the MO content column, Bao, MHO, ZnO, SrO, CaO
The percentage is shown in mol%. Table 4 shows the firing temperature and electrical characteristics of each sample. In this Table 4, the temperature characteristics of capacitance are the capacitance change rate ΔC (%) and ΔC-55 1i5 (%) at -55 °C and +125 °C based on the capacitance at 25 °C, -25 based on capacitance at 20℃
The capacitance change rate at ℃ and +85℃ is shown as ΔC-25 (%) and ΔC85《%). As is clear from Tables 1 to 4, the samples according to the present invention have a dielectric constant ε8 of 3000 when fired in a non-oxidizing atmosphere at 1200°C or less.
Above, dielectric loss tan δ is 2.5% or less, resistivity ρ is IX106MΩ・CI1 or more, temperature change rate of capacitance ΔC-55 and ΔC125 is -15% to +15%,
ΔC-25 and ΔC85 are in the range of -10% to +10%, making it possible to obtain a capacitor with desired characteristics. On the other hand, sample Nail~16, 42, 47, 48, 53, 59
, 62, 65, 68, 71, 74, 77, 78, 82,
83, 87, 88, 96-98, 104, 105, 10
9, 110, 114, 119, and 131 cannot achieve the object of the present invention. Therefore, these are outside the scope of the present invention. Table 4 shows ΔC, ΔC125
, ΔC-25, Δ-55 Only C85 is shown, but the various capacitance change rates ΔC in the range of -25°C to +85°C of samples belonging to the scope of the present invention are -10% to +10%. % range, and
The various capacitance change rates ΔC in the range of -55°C to +125°C are within the range of -15% to +15%. Next, we will discuss the reasons for limiting the composition. xL:y) value is zero as shown in samples NQ88 and 98, ΔC
-25 is outside the range of -10% to +10%, ΔC-55 is -
Although it is outside the range of 15% to +15%, samples NQ89, 9
9, when the value of X is 0.01, desired electrical characteristics can be obtained. Therefore, the lower limit of the value of X is 0.01. On the other hand, samples NQ 9 6, 97, 10
4, when the value of X is 0.12, ΔC85
is outside the range of -10% to +10%, but sample NQ94
, 95, 103, when the value of X is 0.10, desired electrical characteristics can be obtained. Therefore, X
The upper limit of the value of is 0,10. In addition, M component Mg and Z
n works in almost the same way, and the same result can be obtained even if fS1·one selected from these or more than one is used. It is desirable that the value of X be in the range of 0.01 to 0.10 in either case of one type or multiple types of M components. The value of y is for samples NQ59, 62, 65, 6.
As shown in samples No. 8, 71, 74, and 77, a dense sintered body cannot be obtained in the case of 0.06; 5 8, 6
As shown in Figures 1, 64, 67, 70, 73, and 76, desired electrical characteristics can be obtained when the value of y is 0.04. Therefore, the upper limit of the value of y is 0.04. In addition,
R component Sc, Y. Dy, Ho, Er, and Yb work almost in the same way, and the same result can be obtained even if one selected from them is used or a plurality of them are used. And R
Regardless of whether there is one component or multiple components, it is desirable to keep the value of y within the range of 0.04 or less. Also, y
If it is 0.04 or less, even a small amount close to 0 will have some effect. Note that the component indicated by the formula R contributes to improving the temperature characteristics of capacitance. That is, by adding the R component, the temperature change rate of capacitance in the range of -55°C to 125°C is ΔC-5. ~ΔC1.

5 can be easily kept in the range of -15% to +15%, and the temperature change rate of capacitance in the range of -25°C to 85°C is ΔC-25 to ΔC8. -10% to +
It becomes possible to easily keep the capacitance within a range of 10%, and it is also possible to reduce the fluctuation range of the temperature change rate of capacitance in each temperature range. In addition, the R preservative has the effect of increasing the resistivity ρ and the effect of increasing sinterability. As shown in samples NQ78 and 83, when the value of α is zero, ΔC-25 is outside the range of -10% to +10%, and ΔC-5
5 is outside the range of -15% to +15%, but try it! MNn
As shown in 79 and 84, when the value of α is 0.005, desired electrical characteristics can be obtained. Therefore, the lower limit of the value of α is 0.005. On the other hand, sample N082, 8
As shown in 7, when the value of α is 0.05, 8085
is outside the range of -10% to +10%, but sample NQ81
, 86, when the value of α is 0.04, desired electrical characteristics can be obtained. Therefore, the upper limit of the value of α is 0.04. When the value of k is smaller than 61.0 as shown in samples NQ105 and 110, ρ is IXIO MΩ・
Although it is significantly lower than the CI, sample NQI06,
As shown in 111, when the value of k is 1. Desired electrical characteristics can be obtained in the OO stage. Therefore, the lower limit of the value of k is i.
It is oo. On the other hand, the value of k is that of sample No. 1 0 9
, 114, if it is larger than 1.05, ff
Although a dense sintered body could not be obtained, sample No. 99-103
, 108 and 113, desired electrical characteristics can be obtained when the value of k is 1.05. Therefore, the upper limit of the value of k is 1.05. When the amount of additive components added is zero, samples NQ42 and 48
As is clear from the above, even if the firing temperature is 1250°C, a dense sintered body cannot be obtained.
In the case of parts by weight, a sintered body having desired electrical properties can be obtained by firing at 1180 to 1190°C. Therefore, the lower limit of the additive component is 0.2 parts by weight, while sample NQ47
, 53, when the amount of the additive component added is 6.0 parts by weight, ε is less than 3000 and ΔC-5S5 is outside the range of -15% to +15%, but sample NQ4
As shown in 6 and 52, when the amount added is 5. In the case of parts by weight, desired characteristics can be obtained. Therefore, the upper limit of the amount added is 5. Of parts by weight. The preferred composition of the additive components is:
It can be determined based on the triangular diagram showing the composition ratio of L 1 2 03 1 0 2 M O in FIG. The first point (A) in the triangular diagram is sample No. 1-12
The second point (B) is sample k2.
of Lf20 is 1 mol%, SIO2 is 39 mol%,
The third point (C) has a composition of 60 mol % MO, and the third point (C) is sample No. 3 of L 1 2 0 is 30 mol%, S 1
02 shows a composition of 30 mol% and MO 40 mol%,
The fourth point (D) is sample no. 4, L 1 2 0 is 50 mol %, S t O 2 is 50 mol %, MO is O mol %, and the fifth point (B) is Ha.
5 f) Shows a composition of 20 mol % L 1 2 0, 80 mol % SiO2, and 0 mol % MO. The composition of the additive components of the sample that falls within the scope of the present invention is within the area surrounded by five straight lines connecting points 1 to 5 (A) to (E) in the triangular diagram in order. If the combination is within this range, the desired electrical characteristics can be obtained. on the other hand,
If the composition of the additive components falls outside the range specified in the present invention, as in samples 11 to 16, it is not possible to obtain a dense sintered body. Note that the MO component is, for example, sample kl7-21.
(It may be any one of BaO, MgO, ZnO, SrO, CaO, or it may be in an appropriate ratio as shown in other samples. [Modifications] As described above, implementation of the present invention Although the examples have been described, the present invention is not limited thereto, and the following modifications are possible, for example: (a) A trace amount of M n 0 2 (preferably 0.05
~0.1! %) may be added to improve sinterability. In addition, other substances may be added as necessary. (b) The starting materials may be oxides or hydroxides or other compounds other than those shown in the experimental feed. (c) The temperature of the treatment in the oxidizing atmosphere after the treatment in the non-oxidizing atmosphere during firing is lower than the sintering temperature other than 600 °C (preferably in the range of 500 °C to 1000 °C)
It is also possible to do this. That is, it is possible to make various changes in consideration of the electrode material such as nickel and the oxidation of the porcelain. (d) The firing temperature in a non-oxidizing atmosphere can be varied depending on the electrode material. When nickel is used as the internal electrode, almost no agglomeration of nickel particles occurs in the range of 1050°C to 1200″C. (e) Sintering may be performed in a neutral atmosphere. (f)
Of course, it can also be applied to general single-layer ceramic capacitors other than multilayer ceramic capacitors. (g) Tb, Tm, and Lu among the R components in the composition formula are not particularly listed in Tables 1 to 4, but they can be used in the same way as other R components. It has been confirmed.

[Brief explanation of the drawing]

Figure 1 is a sectional view showing a multilayer ceramic capacitor according to an embodiment of the present invention, and Figure 2 is a triangular diagram showing the composition range of additive components. 12... Ceramic layer, 14... Internal electrode, 1 6... External electrode. Agent Noriji Jino

Claims (1)

[Scope of Claims] [1] A ceramic capacitor comprising dielectric ceramic and at least two electrodes in contact with the ceramic, wherein the ceramic contains 100.0 parts by weight of a basic component and 0.2 to 5 parts by weight of a basic component.
．． 0 parts by weight of additional components, and the basic components are (1-α) {(Ba_k_-_xM_x)O_k(Ti
_1_-_yR_y)O_2_-_y_/_2}+αC
aZrO_3 (where M is at least one metal selected from Mg and Zn, R is Sc, Y, Gd, Dy, Ho, Er,
At least one metal among Yb, Tb, Tm, and Lu, α is a numerical value in the range of 0.005 to 0.04, k is a numerical value in the range of 1.00 to 1.05, x is 0.01 to a numerical value in the range of 0.10, y is a numerical value less than or equal to 0.04 and larger than 0), and the additive components are Li_2O, SiO_2, and MO (however,
MO consists of at least one metal oxide of BaO, SrO, CaO, MgO, and ZnO, and the L
The composition range of i_2O, the SiO_2, and the MO is a point (A) where the Li_2O is 1 mol%, the SiO_2 is 80 mol%, and the MO is 19 mol% in a triangular diagram showing these compositions in mol%. , said Li_2
O is 1 mol%, the SiO_2 is 39 mol%, the MO
Point (B) where Li_2O is 60 mol%, point (C) where Li_2O is 30 mol%, SiO_2 is 30 mol%, and MO is 40 mol%, and Li_2O is 50 mol% and the S
Point (D) where iO_2 is 50 mol% and the MO is 0 mol%
, the Li_2O is 20 mol%, and the SiO_2 is 8 mol%.
0 mol %, and the capacitor is within an area surrounded by five straight lines sequentially connecting the point (E) where the MO is 0 mol %. [2] 100.0 parts by weight of basic components and 0.2 to 5.0 parts by weight
parts by weight of additional components, and the basic components are (1-a) {(Ba_k_-_xM_x)O_k(Ti
_1_-_yR_y)O_2_-_y_/_2}+αC
aZrO_3 (where M is at least one metal selected from Mg and Zn, R is Sc, Y, Gd, Dy, Ho, Er,
At least one metal selected from Yb, Tb, Tm, and Lu;
α is a number in the range of 0.005 to 0.04, k is 1.00
~1.05, x is a value in the range of 0.01 to 0.10, y is a value less than or equal to 0.04 and larger than 0), and the additive components are Li_2O, SiO_2, and MO(
However, MO is BaO, SrO, CaO, MgO and Zn
(at least one metal oxide among
Point (A) where i_2O is 1 mol%, SiO_2 is 80 mol%, MO is 19 mol%, and Li_2O is 1 mol%.
mol%, the SiO_2 is 39 mol%, the MO is 60
point (B) where the Li_2O is 30 mol%, the SiO_2 is 30 mol%, and the MO is 40 mol%, and the point (C) where the Li_2O is 50 mol% and the SiO_
Five wires connecting in order the point (D) where 2 is 50 mol% and the MO is 0 mol%, and the point (E) where the Li_2O is 20 mol%, the SiO_2 is 80 mol%, and the MO is 0 mol%. a step of preparing a mixture characterized in that the mixture is within a region surrounded by a straight line; a step of making a molded article of the mixture having at least two electrode portions; and a step of making the molded article having the electrode portions A method for manufacturing a ceramic capacitor, comprising: firing in a non-oxidizing atmosphere; and heat-treating a molded product obtained by the firing in an oxidizing atmosphere.