JPH1192221A - Dielectric porcelain composition and laminated ceramic capacitor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated ceramic capacitor having a high CR product of 5,000 Ω.F at room temperature and a high CR product of >=200 Ω.F at 150 deg.C in an electric field strength of 10 kV/mm, little in the voltage dependency of insulation resistance, excellent in DC bias characteristics and dielectric strength, having temperature characteristics satisfying B characteristics and X7R characteristics, excellent in weather-resistant performance, and using Ni for an inner electrode. SOLUTION: This dielectric porcelain composition for ceramic layers 2a, 2b comprises 100 pts. wt. of a main component of the formula: (Ba0).TiO2 +M2 O3 +R2 O3 +BaZrO3 +MgO+MnO (M2 O3 is Sc2 O3 and/or Y2 O3 ) and 0.2-3.0 pts.wt. of a subsidiary component of the formula: Li2 O-(Si,Ti)O2 -MO (MO is Al2 O3 and/or ZrO2 ) or SiO2 -TiO2 -XO (XO is at least one kind of BaO, CaO, SrO, MgO, ZnO and MnO).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dielectric ceramic composition and a multilayer ceramic capacitor.

[0002]

2. Description of the Related Art Conventionally, a multilayer ceramic capacitor is generally manufactured as follows. First,
A sheet-shaped dielectric material having an electrode material serving as an internal electrode applied to the surface thereof is prepared. As the dielectric material, for example, a material mainly containing BaTiO ₃ is used. Next, the sheet-shaped dielectric material coated with the electrode material is laminated, thermocompression-bonded, and the integrated material is fired at 1250 to 1350 ° C. in an air atmosphere to form a ceramic laminated body having internal electrodes. can get. Then, an external electrode electrically connected to the internal electrode is baked on the end face of the ceramic laminate to obtain a multilayer ceramic capacitor.

Conventionally, noble metals such as platinum, gold, palladium and silver-palladium alloys have been used as materials for the internal electrodes of such multilayer ceramic capacitors. However, although these electrode materials have excellent characteristics, they are expensive, which has been a factor of increasing the manufacturing cost. Therefore, at present, a multilayer capacitor using a base metal Ni as an internal electrode has been proposed in order to reduce the manufacturing cost, and the usage thereof has been increasing.

[0004]

As electronic devices become smaller, more sophisticated, and lower in cost, multilayer ceramic capacitors are becoming lower in cost, higher in dielectric strength, higher in insulation, and more reliable. There is a strong demand for higher capacity and larger capacity.
To reduce the cost of electronic equipment, it is advantageous to use low-cost multilayer ceramic capacitors that use nickel for the internal electrodes.However, conventional dielectric ceramic materials must be used under low electric field strength. Was designed on the assumption that
When used under a high electric field strength, there arises a problem that the insulation resistance value, the dielectric strength and the reliability are extremely reduced. That is, there has been no multilayer ceramic capacitor that can be used under high electric field strength while using nickel for the internal electrode.

More specifically, the dielectric materials disclosed in Japanese Patent Publication No. Sho 57-42588 and Japanese Patent Laid-Open Publication No. Sho 61-101449 have a large dielectric constant, but the crystal grains of the obtained dielectric porcelain can be obtained. As a result, when used under a high electric field strength, the multilayer ceramic capacitor has a drawback that the dielectric strength decreases and the average life time of the high-temperature load test decreases.

In the dielectric material disclosed in Japanese Patent Publication No. 61-14611, the dielectric constant obtained under a low electric field strength is as high as 2000 to 2800, but when used under a high electric field strength, the dielectric constant, that is, the static dielectric constant is low. There is a drawback that the electric capacity is significantly reduced. In addition, there is also a disadvantage that the insulation resistance value is low. Therefore, an object of the present invention is to provide a device in which the insulation resistance is multiplied by the capacitance (CR) when used at a high electric field strength, specifically, a high electric field strength of about 10 kV / mm.
At room temperature and 150 ° C., 4900-5000Ω · F and 190-200Ω · F, respectively.
Above high, the voltage dependence of insulation resistance is small, the stability of capacitance against DC bias voltage is excellent, the dielectric strength is high, and the temperature characteristics of capacitance are stipulated by B characteristics specified by JIS standards and EIA standards To provide a dielectric ceramic composition which satisfies the X7R characteristics described above and has excellent weather resistance performance such as high temperature load and moisture resistance load, for example, which can constitute a dielectric ceramic layer of a multilayer ceramic capacitor. Another object of the present invention is to provide a multilayer ceramic capacitor in which a simple dielectric ceramic composition is used as a dielectric ceramic layer and the internal electrodes are made of Ni or a Ni alloy.

[0007]

In order to achieve the above object, a dielectric porcelain composition of the present invention comprises barium titanate having an alkali metal oxide content of 0.02% by weight or less;
At least one of scandium oxide and yttrium oxide, barium zirconate, consists of a manganese oxide, and the following composition _{formula, {BaO} m TiO 2 +} αM 2 O 3 + βBaZrO 3 +
γMnO (where M ₂ O ₃ is at least one of Sc ₂ O ₃ and Y ₂ O ₃ , α, β and γ represent molar ratios,
0.001 ≦ α ≦ 0.06, 0.005 ≦ β ≦ 0.0
6, 0.001 <γ ≦ 0.13, 1.000 <m ≦ 1.
035. ), And the first subcomponent is Li ₂ O— (Si, Ti) O
_2- MO system (where MO is Al ₂ O ₃ and ZrO ₂
At least one. ), And the second subcomponent is a SiO ₂ —TiO ₂ —XO-based (where XO is Ba)
It is at least one selected from O, CaO, SrO, MgO, ZnO and MnO. ), When one of the first and second subcomponents is
It is characterized in that it is contained in an amount of 0.2 to 3.0 parts by weight based on 100 parts by weight of the main component.

In another aspect, the dielectric porcelain composition of the present invention comprises barium titanate having an alkali metal oxide content of 0.02% by weight or less, at least one of scandium oxide and yttrium oxide, and zirconic acid. It consists of barium, magnesium oxide, and manganese oxide, and has the following composition formula: {BaO} _m TiO ₂ + αM ₂ O ₃ + βBaZrO ₃ +
γMgO + gMnO (where M ₂ O ₃ is at least one of Sc ₂ O ₃ and Y ₂ O ₃ , α, β, γ and g represent molar ratios, and 0.001 ≦ α ≦ 0.06, 0.001 ≦ β ≦ 0.
06, 0.001 <γ ≦ 0.12, 0.001 <g ≦
0.12, γ + g ≦ 0.13, 1.000 <m ≦ 1.0
It is in the range of 35. ) And the first subcomponent is Li ₂ O— (Si, Ti) O ₂
—MO-based (where MO is at least one of Al ₂ O ₃ and ZrO ₂ ) oxides, and the second subcomponent is a SiO ₂ —TiO ₂ —XO-based (where XO is Ba)
It is at least one selected from O, CaO, SrO, MgO, ZnO and MnO. ), When one of the first and second subcomponents is
It is characterized in that it is contained in an amount of 0.2 to 3.0 parts by weight based on 100 parts by weight of the main component.

In the dielectric ceramic composition of the present invention, preferably, the first subcomponent is xLi ₂ O-y (Si _w Ti
_1-w ) O ₂ -zMO (where x, y and z are mol%
And w is in the range of 0.30 ≦ w ≦ 1.0. )
In the ternary composition diagram with each component at the top, A (x = 20, y = 80, z = 0), B (x = 1
0, y = 80, z = 10), C (x = 10, y = 70,
z = 20), D (x = 35, y = 45, z = 20), E
(X = 45, y = 45, z = 10), F (x = 45, y
= 55, z = 0) (However, in the case of the composition on the straight line AF, w is in the range of 0.3 ≦ w <1.0). Inside or on a line.

In the dielectric ceramic composition of the present invention, preferably, the second subcomponent is xSiO ₂ -yTi
When represented by O ₂ -zXO (where x, y and z are mol%), A (x = 85, y = 1, z = 14) of a ternary composition diagram having each component at the top , B (x =
35, y = 51, z = 14), C (x = 30, y = 2)
0, z = 50) and D (x = 39, y = 1, z = 60) are inside or on a line surrounded by a straight line connecting the points.

In the second subcomponent, SiO ₂ —T
Al ₂ O per 100 parts by weight of iO ₂ —XO-based oxide
It is preferred that at least one of ₃ and ZrO ₂ be contained in a total of 15 parts by weight or less (however, ZrO ₂ is 5 parts by weight or less). The present invention is also directed to a multilayer ceramic capacitor including a plurality of dielectric ceramic layers, an internal electrode formed between the dielectric ceramic layers, and an external electrode electrically connected to the internal electrode. . In such a multilayer ceramic capacitor, the dielectric ceramic layer is made of the dielectric ceramic composition according to the present invention as described above, and the internal electrodes are made of nickel or a nickel alloy.

In the multilayer ceramic capacitor according to the present invention, the external electrode includes a sintered layer of a conductive metal powder to which a conductive metal powder or a glass frit is added, or a conductive metal powder or a glass frit. A first layer comprising a sintered layer of conductive metal powder to which is added,
And a second layer comprising a plating layer thereon.

[0013]

First, the basic structure of a multilayer ceramic capacitor according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing an example of the multilayer ceramic capacitor, FIG. 2 is a plan view showing a dielectric ceramic layer portion having internal electrodes in the multilayer ceramic capacitor of FIG. 1, and FIG. FIG. 3 is an exploded perspective view showing a ceramic laminate portion of the capacitor.

As shown in FIG. 1, a multilayer ceramic capacitor 1 according to the present embodiment has a rectangular parallelepiped ceramic laminate obtained by laminating a plurality of dielectric ceramic layers 2a and 2b via internal electrodes 4. 3 is provided. External electrodes 5 are respectively formed on both end surfaces of the ceramic laminate 3 so as to be electrically connected to specific ones of the internal electrodes 4, and a first plating of nickel, copper or the like is formed thereon. A layer 6 is formed, on which a second plating layer 7 of solder, tin or the like is formed.

Next, a method of manufacturing the multilayer ceramic capacitor 1 will be described in the order of manufacturing steps. First, a barium titanate-based raw material powder which is a main component of the dielectric ceramic layers 2a and 2b and is weighed and mixed at a predetermined composition ratio is prepared. That is, as described above, a main component including barium titanate having an alkali metal oxide content of 0.02% by weight or less, at least one of scandium oxide and yttrium oxide, barium zirconate, and manganese oxide; Or barium titanate having an alkali metal oxide content of 0.02% by weight or less, at least one of scandium oxide and yttrium oxide,
It contains a main component consisting of barium zirconate, magnesium oxide and manganese oxide, and contains Li ₂ O—
First subcomponent of (Si, Ti) O ₂ —MO system or Si
A raw material powder containing one of the O ₂ —TiO ₂ —XO-based _second subcomponents and capable of producing a dielectric ceramic composition is prepared.

Next, an organic binder is added to the raw material powder to form a slurry, and the slurry is formed into a sheet to obtain green sheets for the dielectric ceramic layers 2a and 2b. Thereafter, an internal electrode 4 made of nickel or a nickel alloy is formed on one main surface of the green sheet to be the dielectric ceramic layer 2b. If the dielectric ceramic layers 2a and 2b are formed using the above-described dielectric ceramic composition, nickel or a nickel alloy as a base metal can be used as the material of the internal electrodes 4. The internal electrode 4 may be formed by a screen printing method or the like, or may be formed by a vapor deposition method, a plating method, or the like.

Next, after laminating a required number of green sheets for the dielectric ceramic layer 2b having the internal electrodes 4, as shown in FIG. 3, the green sheets for the dielectric ceramic layer 2a having no internal electrodes are formed. Then, the raw laminate is obtained by crimping this. Thereafter, the green laminate is fired at a predetermined temperature in a reducing atmosphere to obtain a ceramic laminate 3.

Next, external electrodes 5 are formed on both end surfaces of the ceramic laminate 3 so as to be electrically connected to the internal electrodes 4. As the material of the external electrode 5, the same material as the internal electrode 4 can be used. Further, silver, palladium, silver-palladium alloy, copper, copper alloy and the like can be used, and B ₂ O ₃ —SiO ₂ —
BaO-based glass, but also used those obtained by adding a glass frit such as Li ₂ O-SiO ₂ -BaO-based glass,
An appropriate material is selected in consideration of a use application, a use place, and the like of the multilayer ceramic capacitor. Further, the external electrode 5 is formed by applying a metal powder paste as a material to the ceramic laminate 3 obtained by firing and baking. However, the external electrode 5 is applied before firing and is baked at the same time as the ceramic laminate 3. It may be formed by the following.

Thereafter, plating of nickel, copper, or the like is performed on the external electrode 5 to form a first plating layer 6. Finally, a second layer of solder, tin, etc. is formed on the first plating layer 6.
Is formed, and the multilayer ceramic capacitor 1 is completed. The formation of a conductor layer on the external electrodes 5 by plating or the like may be omitted depending on the use of the multilayer ceramic capacitor.

As described above, since the dielectric ceramic layers 2a and 2b are formed, by using the above-described dielectric ceramic composition, even when firing in a reducing atmosphere, the characteristics are deteriorated. There is no. That is, 10k
Even when used under a high electric field strength of V / mm,
The product of insulation resistance and capacitance (CR product) is room temperature and 1
At 50 ° C., they are as high as 4900 to 5000 Ω · F and 190 to 200 Ω · F or more, respectively, and the voltage dependence of the insulation resistance is small, and the absolute value of the capacity reduction rate when a DC voltage of 5 kV / mm is applied is 40% to 45%. % And a dielectric strength of 12 kV / mm or more at AC voltage and 14 kV / mm at DC voltage.
mm or higher, and the temperature characteristic of the capacitance is −25 ° C. to +8.
In the range of 5 ° C., the B characteristic specified by the JIS standard and −55
The X7R characteristic specified in the EIA standard is satisfied in the range of from 0 ° C. to + 125 ° C., and characteristics excellent in weather resistance against a high-temperature load of 150 ° C. and 25 kV / mm DC and a load resistant to humidity are obtained.

Sr present as an impurity in barium titanate among the main components of the dielectric ceramic composition
O, alkaline earth metal oxides such as CaO, Na ₂ O,
Alkali metal oxides such as K ₂ O, Al ₂ O ₃ , SiO
Among other oxides such as _2, it has been confirmed that the content of an alkali metal oxide in particular greatly affects electrical characteristics. When the added amount of Sc ₂ O ₃ and Y ₂ O ₃ increases, the relative dielectric constant decreases. However, by reducing the alkali metal oxide present as an impurity in barium titanate to 0.02% by weight or less, The relative dielectric constant can be maintained at 900 to 1600, which has no practical problem.

Further, Li ₂ O—
By adding an oxide of the (Si, Ti) O ₂ -MO system (MO is at least one of Al ₂ O ₃ and ZrO ₂ ), sintering can be performed at a relatively low temperature of 1300 ° C. or less. And high temperature load characteristics can be improved. Further, SiO ₂ —TiO _{2 is} contained in the dielectric ceramic composition.
-XO type (XO is BaO, CaO, SrO, MgO, Z
By adding at least one oxide selected from nO and MnO), sinterability is improved, and high-temperature load characteristics and moisture-resistant load characteristics are improved. Furthermore, Al is added to the SiO ₂ —TiO ₂ —XO-based oxide.
By adding and containing ₂ O ₃ and / or ZrO ₂ , higher insulation resistance can be obtained.

[0023]

EXAMPLES Next, the present invention will be described more specifically based on examples, but embodiments within the scope of the present invention are not limited to only such examples. (Example 1) First, TiC of various purity was used as a starting material.
After preparing and weighing l ₄ and Ba (NO ₃ ) ₂ , titanyl barium oxalate @ BaTiO (C ₂ O ₄ ) with oxalic acid
・ Precipitated as 4H ₂ O｝. This precipitate is 1000
The composition was thermally decomposed at a temperature of not less than ° C. to synthesize four kinds of barium titanate (BaTiO ₃ ) shown in Table 1.

[0024]

[Table 1]

Also, 0.25Li _{2 is used} as the first subcomponent.
_{O-0.65 (0.30TiO 2 · 0.70SiO} 2)
An oxide, carbonate or hydroxide of each component is weighed so as to have a composition ratio of −0.10 Al ₂ O ₃ (molar ratio),
The powder was obtained by mixing and pulverizing. Similarly, 0.66SiO ₂ -0.17TiO ₂ -0.15BaO as a second subcomponent
-0.02MnO (molar ratio)
An oxide, carbonate or hydroxide of each component was weighed and mixed and pulverized to obtain a powder.

Next, the first and second auxiliary component oxide powders are heated to 1500 ° C. in separate platinum crucibles, quenched, and then pulverized to obtain a powder having an average particle diameter of 1 μm or less. An oxide powder was obtained. Next, BaCO ₃ for adjusting the Ba / Ti molar ratio m of barium titanate, and Sc ₂ O ₃ and Y having a purity of 99% or more are used.
₂ O ₃ , BaZrO ₃ , MgO and MnO were prepared. These raw material powders and the oxide powder, which is one of the first and second subcomponents, were weighed to have the compositions shown in Tables 2 and 3. The amount of the first and second sub-components added depends on the amount of the main component [{BaO} _m TiO ₂ + αM ₂ O
₃ + βBaZrO ₃ + γMgO + gMnO] is the number of parts added to 100 parts by weight.

[0027]

[Table 2]

[0028]

[Table 3]

Next, a polyvinyl butyral-based binder and an organic solvent such as ethanol were added to the weighed material, and the mixture was wet-mixed with a ball mill to prepare a ceramic slurry. This ceramic slurry was formed into a sheet by a doctor blade method to obtain a rectangular green sheet having a thickness of 35 μm. Thereafter, a conductive paste mainly composed of Ni was printed on the ceramic green sheet to form a conductive paste layer for forming internal electrodes.

Thereafter, a plurality of ceramic green sheets on which the conductive paste layer was formed were laminated so that the sides from which the conductive paste was drawn out were alternated, to obtain a laminate. This laminate is heated to a temperature of 350 ° C. in an N ₂ atmosphere to decompose the binder, and then the oxygen partial pressure is 10 ⁻⁹ to 1 ^−9.
Calcined for 2 hours at a temperature shown in Table 4 and Table 5 in the 0 ^-12 MPa of H ₂ -N ₂ -H reducing atmosphere consisting of ₂ O gas, to obtain a ceramic sintered body.

After firing, a silver paste containing a glass frit of B ₂ O ₃ —Li ₂ O—SiO ₂ —BaO system was applied to both end surfaces of the obtained ceramic sintered body, and the paste was heated to 600 ° C. in an N ₂ atmosphere. To form an external electrode electrically connected to the internal electrode. The external dimensions of the monolithic ceramic capacitor thus obtained are as follows: width: 5.0
mm, length: 5.7 mm, thickness: 2.4 mm, and the thickness of the dielectric ceramic layer was 30 μm. The total number of effective dielectric ceramic layers was 57, and the area of the counter electrode per layer was 8.2 × 10 ⁻⁶ m ² .

Next, the electrical characteristics of these multilayer ceramic capacitors were measured. The capacitance (C) and the dielectric loss (tan δ) were measured at a frequency of 1 kHz, 1 Vrms and a temperature of 25 ° C. using an automatic bridge type measuring instrument, and the dielectric constant (ε) was calculated from the capacitance. After that, to measure the insulation resistance (R), use an insulation resistance meter to measure
(Ie, 10 kV / mm) and 945 V (ie, 30 kV / mm) DC voltage for 2 minutes
The insulation resistance at 5 ° C. and 150 ° C. was measured, and the product of the capacitance and the insulation resistance, that is, the CR product was determined.

Further, the change rate of the capacitance with respect to the temperature change was measured. The rate of change of the capacitance with respect to the temperature change was −25 ° C. and 85% based on the capacitance at 20 ° C.
° C / C20, and the rate of change (ΔC / C25) between -55 ° C and 125 ° C, based on the capacitance at 25 ° C, and -55 ° C to 125 ° C. The value (| ΔC) at which the rate of change becomes maximum as an absolute value within the range
| Max).

Further, the DC bias characteristics were evaluated. That is, first, the capacitance when an AC voltage of 1 kHz and 1 Vrms was applied was measured. Next, DC150V and 1k
The capacitance was measured when AC voltages of 1 Hz and 1 Vrms were simultaneously applied. Then, the rate of decrease ΔC / C in capacitance due to the application of the DC voltage was calculated. In addition, as a high-temperature load test, 36 samples of each sample were applied with a DC voltage of 750 V (that is, 25 kV / mm) at a temperature of 150 ° C., and the change with time of the insulation resistance was measured. In the high-temperature load life test, the time when the insulation resistance value of each sample became 10 ⁶ Ω or less was defined as the life time, and the average life time was determined.

As a humidity resistance load test, each sample was tested for 72 hours.
The number of samples having an insulation resistance of 10 ⁶ Ω or less when a DC voltage of 315 V was applied for 250 hours at 2 atmospheres (100% relative humidity) and a temperature of 120 ° C. was determined. Further, the breakdown voltage is obtained by applying an AC voltage and a DC voltage at a step-up rate of 100 V / sec, respectively.
The breakdown voltage at the voltage was measured.

The above results are shown in Tables 4 and 5.

[0037]

[Table 4]

[0038]

[Table 5]

As is clear from Tables 1 to 5, the multilayer ceramic capacitor of the present invention has a small capacity reduction ratio of -45% or less when a DC voltage of 5 kV / mm is applied, and a dielectric loss of 1.0% or less. , The rate of change of capacitance with respect to temperature is -2
The range of 5 ° C. to + 85 ° C. satisfies the B characteristic standard specified by the JIS standard, and the range of −55 ° C. to 125 ° C. satisfies the X7R characteristic standard specified by the EIA standard.

In addition, when used under a high electric field strength of 10 kV / mm, the insulation resistance at 25 ° C. and 150 ° C.
When expressed as R product, each is 5000Ω · F or more, 2
The value is as high as 00Ω · F or more. The dielectric breakdown voltage is 12 kV / mm or more at AC voltage and 14 kV / mm at DC voltage.
mm and a large value. In addition, 150 ° C, 25k
The average life time is as long as 800 hours or more in the acceleration test of V / mm, and the firing can be performed at a relatively low temperature of 1300 ° C. or less.

Here, the reasons for limiting the composition of the present invention will be described. {BaO} _m TiO ₂ + αM ₂ O ₃ + βBaZ
rO ₃ + γMgO + gMnO (where M ₂ O ₃ is Sc
_At least one of ₂ O ₃ and Y ₂ O ₃ , α,
β, γ and g represent a molar ratio. In (2), when the amount α of M ₂ O ₃ is less than 0.001 as in sample No. 1, the temperature characteristics do not satisfy the B characteristics / X7R characteristics, which is not preferable. On the other hand, when the amount α of M ₂ O ₃ exceeds 0.06 as in Sample No. 2, the relative dielectric constant decreases to less than 1,000, which is not preferable. Therefore, the amount of M ₂ O ₃ α
Is preferably in the range of 0.001 ≦ α ≦ 0.06.

Further, as shown in Sample No. 3, BaZrO ₃
When the amount β is 0, the insulation resistance is low, and the voltage dependence of the insulation resistance is larger than that of a system containing BaZrO _3, which is not preferable. On the other hand, as shown in Sample No. 4, the amount of BaZrO ₃ β
Exceeds 0.06, the temperature characteristic is also B characteristic / X7
It is not preferable because the R characteristics are not satisfied and the average life time is short. Therefore, the BaZrO ₃ amount β is 0.005 ≦ β ≦
A range of 0.06 is preferred.

When the MgO content γ is 0.001, as in sample No. 5, the insulation resistance is low and the temperature characteristics do not satisfy the B characteristics / X7R characteristics, which is not preferable. On the other hand, when the MgO amount γ exceeds 0.12, as in Sample No. 6,
The sintering temperature increases, the dielectric loss exceeds 2.0%, the number of defectives increases extremely in a moisture resistance load test, and the average life time is undesirably shortened. Therefore, the MgO amount γ is preferably in the range of 0.001 <γ ≦ 0.12.

Further, when the amount g of MnO is 0.001, as in sample No. 7, the measurement cannot be performed due to the semiconductor, which is not preferable. On the other hand, when the MnO amount g exceeds 0.12 as in Sample No. 8, the temperature characteristic X7R is not satisfied, the insulation resistance is low, and the average life time is short, which is not preferable. Therefore, the amount g of MnO is 0.001 <g ≦ 0.
A range of 12 is preferred.

Further, as shown in sample No. 9, MgO and Mn
If the total γ + g of the O content exceeds 0.13, the dielectric loss is increased to 2.0% or more, the average life time is shortened, and the number of failures in the moisture resistance load test is undesirably increased. Therefore, the total γ + g of the amounts of MgO and MnO is γ + g
The range of g ≦ 0.13 is preferred. Further, when the BaO / TiO ₂ ratio m is less than 1.000 as in Sample No. 10, the measurement cannot be performed because of the semiconductor, which is not preferable. Further, when the BaO / TiO ₂ ratio m is 1.000 as in Sample No. 11, the insulation resistance is low, the AC and DC breakdown voltages are low, and the average life time is short, which is not preferable. On the other hand, as in Sample Nos. 12 and 13, BaO / TiO
_{When the} ratio m exceeds 1.035, measurement becomes impossible due to insufficient sintering, which is not preferable. Therefore, BaO / TiO
_The ratio m is preferably in the range of 1.000 <m ≦ 1.035.

As shown in sample numbers 14 and 16,
The addition amount of the first subcomponent or the addition amount of the second subcomponent is 0
In case (1), measurement is impossible due to insufficient sintering, which is not preferable.
On the other hand, as in Sample Nos. 15 and 17, when the added amount of the first subcomponent or the added amount of the second subcomponent exceeds 3.0 parts by weight, the dielectric loss exceeds 1.0%, and In addition, the insulation resistance and the breakdown voltage are low, and the average lifetime is undesirably short. Therefore, the content of either the first or second subcomponent is preferably in the range of 0.2 to 3.0 parts by weight.

Further, the content of the alkali metal oxide contained as an impurity in the barium titanate was set to 0.02% by weight or less, as shown in Sample No. 18, when the content of the alkali metal oxide was 0.1%. If it exceeds 02% by weight,
This is because a decrease in the dielectric constant occurs. (Example 2) as a dielectric powder, using a barium titanate A in Table _{1, BaO 1.010 · TiO 2 +} 0.03Y
₂ O ₃ + 0.02BaZrO ₃ + 0.05MgO + 0.
A raw material of 01MnO (molar ratio) was prepared, and 120
A Li ₂ O— (Si, Ti) O ₂ —MO-based oxide having an average particle size of 1 μm or less shown in Table 6 prepared by heating at 0 to 1500 ° C. was added as a first subcomponent. A multilayer ceramic capacitor was manufactured in the same manner as in Example 1.
The dimensions and shape of the manufactured multilayer ceramic capacitor are the same as those in the first embodiment.

[0048]

[Table 6]

Next, the electrical characteristics were measured in the same manner as in Example 1. Table 7 shows the results.

[0050]

[Table 7]

As is clear from Tables 6 and 7, FIG.
In the ternary composition diagram of the Li ₂ O— (Si _w Ti _1-w ) O ₂ —MO system oxide shown in FIG.
0), B (x = 10, y = 80, z = 10), C (x =
10, y = 70, z = 20), D (x = 35, y = 4)
5, z = 20), E (x = 45, y = 45, z = 1)
0), F (x = 45, y = 55, z = 0) (provided that
x, y, and z are mol%, w is a molar ratio, and in the case of a composition on a straight line AF, w is a straight line connecting points indicated by 0.3 ≦ w <1.0). Sample Nos. 101 to 112, 1 to which the oxides inside or on the line in the enclosed area were added
18 and 120, the rate of decrease in capacitance when a DC voltage of 5 kV / mm is applied is as small as -45% or less, the dielectric loss is 1.0% or less, and the rate of change of capacitance with temperature is -2.
A preferable result is obtained in which the B characteristic standard defined in the JIS standard is satisfied in the range of 5 ° C. to 85 ° C., and the X7R characteristic standard defined in the EIA standard is satisfied in the range of −55 ° C. to 125 ° C.

In addition, when used under a high electric field strength of 10 kV / mm, when the insulation resistance at 25 ° C. and 150 ° C. is represented by a CR product, the resistance is 5000Ω · F or more and 200Ω or more, respectively.
It shows a high value of Ω · F or more. Also, if the breakdown voltage is AC
12 kV / mm or more in voltage, 14 kV / mm in DC voltage
The above shows a large value. Further, at 150 ° C. and 25 kV /
The average life time is as long as 800 hours or more in the accelerated test of mm, and the firing can be performed at a relatively low temperature of 1300 ° C. or less.

On the other hand, Li ₂ O— (Si _w Ti
_1-w ) When the O ₂ -MO-based oxide is out of the above composition range, as shown in Sample Nos. 113 to 117 and 119, sintering becomes insufficient, or even if sintering, a failure in a moisture resistance load test results. Occur. Also, the composition on points AF and w =
In the case of 1.0, the sintering temperature becomes high as in sample numbers 119 and 121, and a failure occurs in the moisture resistance load test. When the value of w is less than 0.30, as shown in sample number 122, the sintering temperature increases, and a failure occurs in the moisture resistance load test.

(Example 3) As a dielectric powder, A in Table 1 was used.
BaO _1.010 · TiO ₂ using barium titanate
+ 0.03Sc ₂ O ₃ + 0.015BaZrO ₃ +0.
A raw material of 05MgO + 0.01MnO (molar ratio) was prepared, and heated at 1200 to 1500 ° C., and SiO ₂ —TiO ₂ — having an average particle size of 1 μm or less shown in Table 8 was prepared.
A multilayer ceramic capacitor was manufactured in the same manner as in Example 1, except that an XO-based oxide was added as a second subcomponent. Each additive amount of Al ₂ O ₃ and ZrO _2, the second subcomponent [xSiO ₂ -yTiO ₂ -zXO]
It is the number of parts added to 100 parts by weight. The external dimensions of the manufactured multilayer capacitor are the same as those of the first embodiment.

[0055]

[Table 8]

Next, the electrical characteristics were measured in the same manner as in Example 1. Table 9 shows the results.

[0057]

[Table 9]

As is clear from Tables 8 and 9, FIG.
A (x = 85, y = 1, z = 14) and B (x = 3) in the ternary composition diagram of the SiO ₂ —TiO ₂ —XO-based oxide shown in FIG.
5, y = 51, z = 14), C (x = 30, y = 20,
z = 50) and D (x = 39, y = 1, z = 60) (where x, y, and z are mol%) within or on a region surrounded by a straight line connecting points. Samples 201 to 212 to which the oxide was added had a D of 5 kV / mm.
The capacitance reduction rate when applying a C voltage is as small as -45% or less, the dielectric loss is 1.0% or less, and the rate of change of capacitance with respect to temperature is in the range of -25 ° C to 85 ° C.
Satisfies the characteristic specifications and EI within the range of -55 ° C to 125 ° C
A favorable result of satisfying the X7R characteristic standard defined in the A standard is obtained.

In addition, when used at a high electric field strength of 10 kV / mm, when the insulation resistance at 25 ° C. and 150 ° C. is expressed by CR product, it is 5000 Ω · F or more and 200 Ω · F or more, respectively.
It shows a high value of Ω · F or more. Also, if the breakdown voltage is AC
12 kV / mm or more in voltage, 14 kV / mm in DC voltage
The above shows a large value. Further, at 150 ° C. and 25 kV /
The average life time is as long as 800 hours or more in the accelerated test of mm, no failure is observed in the moisture resistance load test, and the firing can be performed at a relatively low temperature of 1300 ° C. or lower.

On the other hand, SiO ₂ —TiO ₂ —XO
If the system oxide is out of the above composition range, sample number 213
As shown in FIGS. 219 to 219, sintering becomes insufficient, or even if sintering occurs, a failure occurs in a moisture resistance load test. Sample No. 2
As in 11 and 212, SiO ₂ —TiO ₂ —XO
By adding Al ₂ O ₃ and / or ZrO ₂ to the system oxide, the insulation resistance at 25 ° C. and 150 ° C. under an electric field strength of 10 kV / mm is 5400 Ω · F, 300
A multilayer capacitor of Ω · F or more can be obtained.
17 and 218, the amount of Al ₂ O ₃ added is 1
If the amount exceeds 5 parts by weight and the amount of ZrO ₂ exceeds 5 parts by weight, the sinterability is extremely reduced.

(Embodiment 4) A method similar to that of Embodiment 1 is used.
The four types of barium titanate (BaTi
O _Three), An oxide powder as a first subcomponent, and a second
An oxide powder was obtained as a subcomponent of Next, titanate
BaCO for adjusting the Ba / Ti molar ratio m of lithium
_ThreeAnd Sc with a purity of 99% or more_TwoO_Three, Y_TwoO_Three, BaZ
rO_ThreeAnd MnO were prepared. These raw material powders and
The above oxide, which is one of the first and second subcomponents
The powder was weighed so as to have the composition shown in Tables 10 and 11.
did. The amount of the first and second subcomponents added depends on the amount of the main component.
[{BaO}_mTiO_Two+ ΑM_TwoO_Three+ ΒBaZrO_Three
+ ΓMnO] is the number of parts added to 100 parts by weight. So
Then, using this weighed material, the same method as in Example 1 was used.
Thus, a multilayer ceramic capacitor was manufactured. Also make
The external dimensions of the laminated ceramic capacitor
Same as Example 1.

[0062]

[Table 10]

[0063]

[Table 11]

Next, the electrical characteristics were measured in the same manner as in Example 1. The results are shown in Tables 12 and 13.

[0065]

[Table 12]

[0066]

[Table 13]

As is apparent from Tables 10 to 13, the multilayer ceramic capacitor of the present invention has a small capacity reduction rate of -40% or less when a DC voltage of 5 kV / mm is applied, and a dielectric loss of 1.0% or less. When the rate of change of the capacitance with respect to the temperature is in the range of -25 ° C to + 85 ° C, it satisfies the B characteristic standard stipulated in the JIS standard, and in the range of -55 ° C to 125 ° C, it satisfies the X7R characteristic standard stipulated in the EIA standard. I do.

Furthermore, when used under a high electric field strength of 10 kV / mm, the insulation resistance at 25 ° C. and 150 ° C.
When expressed as R product, each is 4900Ω · F or more, 1
It shows a high value of 90Ω · F or more. The dielectric breakdown voltage is 12 kV / mm or more at AC voltage and 14 kV / mm at DC voltage.
mm and a large value. In addition, 150 ° C, 25k
The average life time is as long as 800 hours or more in the acceleration test of V / mm, and the firing can be performed at a relatively low temperature of 1300 ° C. or less.

Here, the reasons for limiting the composition of the present invention will be explained.
I will tell. {BaO}_mTiO_Two+ ΑM_TwoO_Three+ ΒBaZ
rO_Three+ ΓMnO (however, M _TwoO_ThreeIs Sc_TwoO_ThreeAnd
And Y_TwoO_ThreeΑ, β and γ are at least one of
Represents the molar ratio. ), As in sample number 301,
M_TwoO_ThreeWhen the amount α is less than 0.001, the temperature characteristic
B characteristics / X7R characteristics are not satisfied, which is not preferable. one
On the other hand, M_TwoO_ThreeAmount α is 0.06
If it exceeds, the relative permittivity decreases to less than 900.
Not preferred. Therefore, M_TwoO_ThreeThe amount α is 0.001
The range of ≦ α ≦ 0.06 is preferable.

Further, as shown in sample number 303, BaZr
When the O ₃ amount β is 0, the insulation resistance is low and BaZrO
_This is not preferable because the voltage dependence of the insulation resistance is larger than that of a system containing ₃ . On the other hand, BaZr
When the amount of O ₃ exceeds 0.06, the temperature characteristics do not satisfy the B characteristics / X7R characteristics, and the average life time is short, which is not preferable. Therefore, the BaZrO ₃ amount β is 0.00
The range of 5 ≦ β ≦ 0.06 is preferable.

When the MgO content γ is 0.001, as in sample No. 305, it is not preferable because it cannot be measured because of the semiconductor. On the other hand, as shown in sample number 306, MgO
When the amount γ exceeds 0.13, the temperature characteristic X7R is not satisfied, the insulation resistance is low, and the average life time is undesirably short. Therefore, the MgO amount γ is 0.001 <γ ≦
A range of 0.13 is preferred.

As shown in sample number 307, BaO /
If the TiO ₂ ratio m is less than 1.000, measurement becomes impossible due to semiconductor conversion, which is not preferable. Further, when the BaO / TiO ₂ ratio m is 1.000 as in Sample No. 308, the insulation resistance is low, the AC and DC breakdown voltages are low, and the average life time is short. On the other hand, as shown in sample numbers 309 and 310, the BaO / TiO ₂ ratio m was 1.03.
If it exceeds 5, measurement becomes impossible due to insufficient sintering, which is not preferable. Therefore, the BaO / TiO ₂ ratio m is 1.00.
The range of 0 <m ≦ 1.035 is preferable.

Further, when the addition amount of the first sub-component or the addition amount of the second sub-component is 0 as in sample numbers 311 and 313, the measurement becomes impossible due to insufficient sintering, which is not preferable. On the other hand, as shown in sample numbers 312 and 314, the first
The amount of the subcomponent added or the amount of the second subcomponent added is 3.0.
If the amount is more than 10 parts by weight, the dielectric loss exceeds 1.0%, the insulation resistance and the breakdown voltage are low, and the average life time is undesirably short. Therefore, the first or second
Is preferably in the range of 0.2 to 3.0 parts by weight.

Further, the content of the alkali metal oxide contained as an impurity in the barium titanate was set to 0.02% by weight or less, as in Sample No. 315, when the content of the alkali metal oxide was 0.1%. If it exceeds 02% by weight, the dielectric constant will be reduced. (Example 5) as a dielectric powder, using a barium titanate A in Table _{1, BaO 1.010 · TiO 2 +} 0.02Y
A raw material of ₂ O ₃ +0.01 BaZrO ₃ +0.04 MnO (molar ratio) was prepared and heated at 1200 to 1500 ° C., and the same average particle size as shown in Table 6 was prepared, and the average particle diameter was 1 μm.
A multilayer ceramic capacitor was manufactured in the same manner as in Example 1 except that the following Li ₂ O— (Si, Ti) O ₂ —MO-based oxide was added as a first subcomponent. In addition,
The dimensions and shape of the manufactured multilayer ceramic capacitor are the same as those in the first embodiment. Then, the electrical characteristics were measured in the same manner as in Example 1. Table 14 shows the results. Table 1
In FIG. 4, sample numbers 401 to 422 correspond to sample numbers 101 to 122 in Table 6, respectively. For example, sample number 401 in Table 14 corresponds to sample number 101 in Table 6.
Obtained by adding the subcomponent of

[0075]

[Table 14]

Li ₂ O— (Si _w Ti _1-w ) shown in FIG.
A (x = 20, y) in the ternary composition diagram of the O ₂ —MO-based oxide
= 80, z = 0), B (x = 10, y = 80, z = 1)
0), C (x = 10, y = 70, z = 20), D (x =
35, y = 45, z = 20), E (x = 45, y = 4)
5, z = 10), F (x = 45, y = 55, z = 0)
(However, x, y, and z are mol%, w is a molar ratio, and in the case of a composition on a straight line AF, w is in the range of 0.3 ≦ w <1.0). Sample numbers 101 to 112, 11 in Table 6 inside or on the area surrounded by the connecting straight line
Samples 401 to 412, 418 and 4 in Table 14 were prepared by adding oxides 8 and 120 as subcomponents.
As shown in FIG. 20, the rate of capacitance decrease when a DC voltage of 5 kV / mm is applied is as small as -40% or less, the dielectric loss is 1.0% or less, and the rate of change of capacitance with temperature is-.
A preferable result is obtained in which the B characteristic standard defined in the JIS standard is satisfied in the range of 25 ° C to 85 ° C, and the X7R characteristic standard defined in the EIA standard is satisfied in the range of -55 ° C to 125 ° C.

Further, when used under a high electric field strength of 10 kV / mm, when the insulation resistance at 25 ° C. and 150 ° C. is represented by a CR product, it is 4900 Ω · F or more, respectively.
It shows a high value of Ω · F or more. Also, if the breakdown voltage is AC
12 kV / mm or more in voltage, 14 kV / mm in DC voltage
The above shows a large value. Furthermore, 150 ° C, DC 25k
The average life time is as long as 800 hours or more in the acceleration test of V / mm, and the firing can be performed at a relatively low temperature of 1300 ° C. or less.

On the other hand, sample numbers 113 to 1 in Table 6
17 and 119, Li ₂ O— (Si _w Ti
_1-w ) When the O ₂ -MO-based oxide is out of the above composition range, as shown in the sample numbers 413 to 417 and 419 of Table 14, the sintering is insufficient or the sintering does not provide moisture resistance. Failure occurs in the load test. Further, as shown in the sample numbers 119 and 121 in Table 6, when the composition on the points A to F and w = 1.0, as seen in the sample numbers 419 and 421 in Table 14, the sintering temperature was lowered. High, and failure occurs in the moisture resistance load test. Table 6
In the case where the value of w is less than 0.30 as in Sample No. 122, the sintering temperature increases as shown in Sample No. 422 in Table 14, and a failure occurs in the moisture resistance load test.

(Example 6) As a dielectric powder, A in Table 1 was used.
BaO _1.010 · TiO ₂ using barium titanate
+ 0.02Sc ₂ O ₃ + 0.01BaZrO ₃ +0.0
A raw material of 4MnO (molar ratio) was prepared, and
Example 1 was prepared by adding a SiO ₂ —TiO ₂ —XO-based oxide having an average particle size of 1 μm or less similar to that shown in Table 8 produced as a result of heating at ℃ 1500 ° C. as a second auxiliary component.
A multilayer ceramic capacitor was produced in the same manner as described above. The external dimensions of the manufactured multilayer capacitor are the same as those of the first embodiment. Then, the electrical characteristics were measured in the same manner as in Example 1. Table 15 shows the results. In Table 15, sample numbers 501 to 519 correspond to sample numbers 201 to 219 in Table 8, respectively.
Sample No. 501 of No. 5 was obtained by adding the subcomponent of Sample No. 201 of Table 8.

[0080]

[Table 15]

A (x = 85, y = 1, z = 1) in the ternary composition diagram of the SiO ₂ —TiO ₂ —XO-based oxide shown in FIG.
4), B (x = 35, y = 51, z = 14), C (x =
30, y = 20, z = 50), D (x = 39, y = 1,
z = 60) (where x, y, and z are mol%) oxides of Sample Nos. 201 to 212 in Table 8 inside or on the line surrounded by a straight line connecting the points as subcomponents As shown in Sample Nos. 501 to 512 in Table 15, the added one has a small capacity reduction rate of -40% or less when a 5 kV / mm DC voltage is applied, and a dielectric loss of 1.0%.
% Or less, the rate of change of the capacitance with respect to temperature is -25 ° C.
A preferable result is obtained in which the B characteristic standard defined in the JIS standard is satisfied in the range of 85 ° C, and the X7R characteristic standard defined in the EIA standard is satisfied in the range of -55 ° C to 125 ° C.

In addition, when used at a high electric field strength of 10 kV / mm, when the insulation resistance at 25 ° C. and 150 ° C. is expressed by CR product, it is 4900 Ω · F or more and 190
It shows a high value of Ω · F or more. Also, if the breakdown voltage is AC
12 kV / mm or more in voltage, 14 kV / mm in DC voltage
The above shows a large value. Furthermore, 150 ° C, DC 25k
The average life time is as long as 800 hours or more in the V / mm acceleration test, no failure is observed in the moisture resistance load test, and the firing can be performed at a relatively low temperature of 1300 ° C. or less.

On the other hand, sample numbers 213 to 2 in Table 8
As in 19, SiO_Two-TiO_Two-XO-based oxide
When the composition is outside the above composition range, sample numbers 513 to 5 in Table 15 are used.
As can be seen in FIG.
Even in the humidity resistance load test, a defect occurs. Also, the table
8, sample numbers 211 and 212_Two−
TiO_Two-XO-based oxide, Al_TwoO_ThreeAnd / or
Is ZrO_Two, The sample number 51 in Table 15
As in 1 and 512, under an electric field strength of 10 kV / mm
The insulation resistance at 25 ° C and 150 ° C is 5290Ω
F, a multilayer capacitor of 310Ω · F or more can be obtained.
Further, as shown in sample numbers 217 and 218 of Table 8, A
l _TwoO_Three15 parts by weight and ZrO_TwoAmount added
If it exceeds 5 parts by weight, the sample numbers 517 and
And 518, the sinterability is extremely reduced.

As described above, in each of the examples, the barium titanate used was a powder produced by the oxalic acid method. However, the present invention is not limited to this. For example, barium titanate powder produced by the alkoxide method or hydrothermal synthesis is used. May be used. By using these powders, the characteristics of the multilayer ceramic capacitor may be improved more than the characteristics shown in the above-described embodiments.

As a starting material, Sc was used._TwoO_Three, Y_Two
O_Three, MgO, MnO, BaZrO _ThreeOxide powder such as
However, the present invention is not limited to this,
To constitute a dielectric ceramic layer within the scope of the present invention
If mixed, use a solution of alkoxide, organic metal, etc.
However, this does not impair the characteristics obtained.

[0086]

As is clear from the above description, according to the dielectric ceramic composition of the present invention, it is not reduced even when fired in a reducing atmosphere, does not turn into a semiconductor, and has a temperature lower than 1300 ° C. It can be sintered at very low temperature. Therefore, if this dielectric ceramic composition is used as a dielectric ceramic layer to constitute a multilayer ceramic capacitor, nickel or a nickel alloy, which is a base metal, can be used as an electrode material. Down can be planned.

Further, the multilayer ceramic capacitor using this dielectric ceramic composition has a low insulation resistance in a conventional multilayer ceramic capacitor using nickel or a nickel alloy for the internal electrode, and has a reliability of 10 kV.
/ Mm, when the insulation resistance is expressed as the product of the capacitance and the capacitance (CR product), the room temperature and 1
Insulation resistance at 50 ° C is 4900-5000Ω.
F, which is as high as 190 to 200 Ω · F or more, the voltage dependence of insulation resistance is small, the absolute value of the capacity reduction rate when a DC voltage of 5 kV / mm is applied is as small as 40 to 45% or less, the dielectric strength is high, and The temperature characteristics of the capacitance are stipulated by JIS standards B
Satisfies the characteristics and X7R characteristics specified by EIA standard,
It is possible to obtain a multilayer ceramic capacitor excellent in weather resistance such as a high temperature load of 150 ° C., a DC voltage of 25 kV / mm applied and a moisture resistance load.

[Brief description of the drawings]

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

FIG. 2 is a plan view showing a dielectric ceramic layer portion having internal electrodes in the multilayer ceramic capacitor of FIG. 1;

FIG. 3 is an exploded perspective view showing a ceramic laminate portion of the multilayer ceramic capacitor of FIG. 1;

FIG. 4 is a ternary composition diagram of a Li ₂ O— (Si _w Ti _1-w ) O ₂ —MO-based oxide.

FIG. 5 is a ternary composition diagram of an SiO ₂ —TiO ₂ —XO-based oxide.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Multilayer ceramic capacitor 2a, 2b Dielectric ceramic layer 3 Ceramic laminated body 4 Internal electrode 5 External electrode 6, 7 Plating layer

Claims (8)

[Claims] 1. An alkali metal oxide content of 0.02
% By weight of barium titanate, at least one of scandium oxide and yttrium oxide, barium zirconate and manganese oxide, and has the following composition formula: {BaO} _m TiO ₂ + αM ₂ O ₃ + βBaZrO ₃ +
γMnO (where M ₂ O ₃ is at least one of Sc ₂ O ₃ and Y ₂ O ₃ , α, β and γ represent molar ratios, and 0.001 ≦ α ≦ 0.06 0.005 ≦ β ≦ 0.06 0.001 <γ ≦ 0.13 1.000 <m ≦ 1.035), and the first subcomponent is Li ₂ O— ( Si, Ti) O ₂ -M
An O-based oxide (where MO is at least one of Al ₂ O ₃ and ZrO ₂ ), and the second subcomponent is S
iO ₂ —TiO ₂ —XO system (where XO is BaO, C
It is at least one selected from aO, SrO, MgO, ZnO and MnO. ), Wherein one of the first and second subcomponents is contained in an amount of 0.2 to 3.0 parts by weight based on 100 parts by weight of the main component. A dielectric ceramic composition. 2. An alkali metal oxide content of 0.02
% Of barium titanate, at least one of scandium oxide and yttrium oxide, barium zirconate, magnesium oxide and manganese oxide, and has the following composition formula: {BaO} _m TiO ₂ + αM ₂ O ₃ + βBaZrO ₃ +
γMgO + gMnO (where M ₂ O ₃ is at least one of Sc ₂ O ₃ and Y ₂ O ₃ , α, β, γ and g represent a molar ratio, and 0.001 ≦ α ≦ 0.06 0.001 ≦ β ≦ 0.06 0.001 <γ ≦ 0.12 0.001 <g ≦ 0.12 γ + g ≦ 0.13 1.000 <m ≦ 1.035) And the first subcomponent is Li ₂ O— (Si, Ti) O ₂ —M
An O-based oxide (where MO is at least one of Al ₂ O ₃ and ZrO ₂ ), and the second subcomponent is S
iO ₂ —TiO ₂ —XO system (where XO is BaO, C
It is at least one selected from aO, SrO, MgO, ZnO and MnO. ), Wherein one of the first and second subcomponents is contained in an amount of 0.2 to 3.0 parts by weight based on 100 parts by weight of the main component. A dielectric ceramic composition. 3. The method according to claim 1, wherein the first subcomponent is xLi._TwoO-y
(Si_wTi_1-w) O _Two-ZMO (however, x, y and
And z are mol%, w is in the range of 0.30 ≦ w ≦ 1.0
Is within. ), Each component is defined as a vertex
A (x = 20, y = 80, z = 0) B (x = 10, y = 80, z = 10) C (x = 10, y = 70, z = 20) D ( x = 35, y = 45, z = 20) E (x = 45, y = 45, z = 10) F (x = 45, y = 55, z = 0) (However, the composition on the straight line AF) In the case of, w is 0.3 ≦
(within w <1.0) surrounded by a straight line connecting the points
Inside or on the line of the
3. The dielectric porcelain composition according to claim 1 or 2. 4. The method according to claim 1, wherein the second subcomponent is xSiO ₂ -yT
When represented by iO ₂ -zXO (where x, y and z are mol%), A (x = 85, y = 1, z = 14) of a ternary composition diagram having each component at the top B (x = 35, y = 51, z = 14) C (x = 30, y = 20, z = 50) D (x = 39, y = 1, z = 60) A straight line connecting the points indicated by 3. The dielectric porcelain composition according to claim 1, wherein the dielectric porcelain composition is located inside or on a line surrounded by. 5. The method according to claim 1, wherein the second sub-component comprises the SiO ₂
-TiO ₂ -XO series Al on the oxide 100 parts by weight of
₂ O ₃ and ZrO ₂ at least one of a total of 15 parts by weight or less (however, less ZrO ₂ is 5 parts by weight), characterized in that it contains a dielectric ceramic composition according to claim 4. 6. A multilayer ceramic capacitor, comprising: a plurality of dielectric ceramic layers; an internal electrode formed between the dielectric ceramic layers; and an external electrode electrically connected to the internal electrode. A multilayer ceramic capacitor, wherein a ceramic layer is made of the dielectric ceramic composition according to any one of claims 1 to 5, and the internal electrode is made of nickel or a nickel alloy. 7. The multilayer ceramic capacitor according to claim 6, wherein the external electrode includes a sintered layer of a conductive metal powder or a conductive metal powder to which glass frit is added. 8. The external electrode includes a first layer made of a sintered layer of a conductive metal powder or a conductive metal powder to which glass frit is added, and a second layer made of a plating layer thereon. The multilayer ceramic capacitor according to claim 6, wherein: