JPH03278418A - Porcelain capacitor and manufacture thereof - Google Patents

Abstract

PURPOSE:To improve relative permittivity by mixing 100 pts.wt. of specific basic component, and 0.01-3 pts.wt. of first specific additive component, and 0.2-5 pts.wt. of second specific additive components of specific ranges of a triangular diagram of mol% of composition range, and firing the mixture to form a dielectric porcelain composition. CONSTITUTION:100 pts.wt. of basic component represented by formula I, 0.01-3 pts.wt. of additive component containing Cr2O3 and/or AlO3 and 0.2-5 pts.wt. of second additive component containing Li2O, SiO2 and MO (MO is metal oxide of one or more types selected from BaO, SrO, CaO, MgO and ZnO) and mixed and fired. The composition range of the second additive component is disposed in a range surrounded by straight lines for sequentially coupling points A-B-C-D-E-A of a triangular diagram shown by mole % of the composition range of the additive component, and hence dielectric porcelain composition having 3000 or more of its relative permittivity can be formed. In formula I, M; Mg and/or Zn, R; one or more types or metal elements selected from Sc, Y, Gd, Dy, Ho, Er, Yb. Letters k, x, y, z; numerical values for satisfying formulae II, III, IV, V, VI.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a ceramic capacitor having a single-layer or laminated structure in which a dielectric ceramic layer is sandwiched between at least two internal electrodes, and a method for manufacturing the same. .

[Prior Art] Conventionally, when manufacturing multilayer ceramic capacitors, a conductive paste of noble metal such as platinum or palladium is printed in a desired pattern on an unsintered porcelain sheet (green sheet) made of dielectric porcelain raw material powder. A plurality of these sheets were stacked and pressed together, and fired at 1300°C to 1600°C in an oxidizing atmosphere.

Through this firing, the unsintered porcelain sheet made of the dielectric porcelain raw material powder becomes a dielectric porcelain layer, and the conductive paste of noble metal such as platinum or palladium becomes an internal electrode.

As mentioned above, if a conductive paste containing a noble metal such as platinum or palladium is used as the main component, the intended internal electrode can be formed even if it is fired at a high temperature of 1300°C to 1600°C in an oxidizing atmosphere. Obtainable.

However, since precious metals such as platinum and palladium are expensive, the cost of multilayer ceramic capacitors has inevitably increased.

Japanese Patent Publication No. 14607/1983, filed by the applicant, discloses (B
a M−M If] Om T i O2 (where M is Mg and/or Zn), and L i z
A dielectric ceramic composition is disclosed that includes an additive component consisting of O and Sing.

In addition, Japanese Patent Publication No. 61-14608 discloses that the dielectric ceramic composition described in Japanese Patent Publication No. 61-14607 is
Instead of it O and S i Ox, L i s
O, S i Oz and MO (however, MO is BaO, Ca
A dielectric ceramic composition is disclosed that includes an additive component consisting of one or more gold oxides selected from O and SrO.

In addition, in Japanese Patent Publication No. 14609/1983, (Bak
-x-y Mx Ly) Oi+ 710x (However,
A dielectric ceramic composition is disclosed that includes a basic component in which M is Mg and/or Zn, and L is Sr and/or Ca, and additional components include Li2O and 5i02.

Further, in Japanese Patent Publication No. 61-14610, in place of Li*O and 5iOz in the dielectric ceramic composition described in Japanese Patent Publication No. 61-14609,
, Sing, and MO (where MO is one or more metal oxides selected from BaO, CaO, and SrO).

In addition, in Japanese Patent Publication No. 14611/1983, (B ai
+-++ MWlol 7 i Ox (However, M is Mg.

A dielectric ceramic composition is disclosed that includes a basic component consisting of one or more metal elements selected from Zn + Sr and Ca) and an additive component consisting of B2O and SiOa. .

Furthermore, in Japanese Patent Publication No. 1595/1983, (B a, -
x MXIOII T 10K (However, M is Mg.

one or more metal elements selected from Zn, Sr and Ca); and B20. and MO(
However, MO is Bao.

A dielectric ceramic composition containing an additive component consisting of one or more metal oxides selected from MgO, ZnO, SrO, and CaO is disclosed.

In addition, Japanese Patent Publication No. 1596/1983 describes the B2O of the dielectric ceramic composition described in Japanese Patent Publication No. 1595/1982.
3 and BaO, instead of MO.

SiO2 and MO (However, MO is Bad.

A dielectric ceramic composition containing an additive component consisting of one or more metal oxides selected from MgO, ZnO, SrO, and CaO is disclosed.

If the dielectric ceramic composition disclosed in these documents is used as a dielectric layer, it can be heated to 1000°C in a reducing atmosphere.
Porcelain capacitors can be obtained by firing at temperatures below,
Moreover, the relative permittivity of the dielectric ceramic composition is 2000 or more, and the temperature change rate of the relative permittivity is 11 from -25°C to +85°C.
It can be in the range of 0% to +1O%.

[Problems to be solved by the invention] By the way, with the increasing density of electronic circuits in recent years,
There is a very strong demand for miniaturization of ceramic capacitors, and it has been desired to develop a ceramic capacitor equipped with a dielectric ceramic composition having a higher dielectric constant than the dielectric ceramic compositions disclosed in the above-mentioned publications. .

In addition, since ceramic capacitors are used in various environments, they are equipped with a dielectric ceramic composition that has a smaller rate of change in relative dielectric constant over a wider temperature range than the dielectric ceramic compositions disclosed in the above-mentioned publications. There was a desire to develop a ceramic capacitor that would

Therefore, the object of the present invention is to
Although it can be obtained by firing at temperatures below 200°C, it has a relative dielectric constant of 3000 or more and a dielectric loss tan δ of 2.
．． 5% or less, the resistivity ρ is 1xlO'MΩ・cm or more, and the temperature change rate of the dielectric constant is -15% to +15% (based on 25°C) at -55°C to 125°C, -25°C to 85
The object of the present invention is to provide a ceramic capacitor equipped with a dielectric ceramic composition whose temperature ranges from -10% to +10% (based on 20°C) and a method for manufacturing the same.

[Means for Solving the Problems] A ceramic capacitor according to the present invention includes a dielectric ceramic layer made of a dielectric ceramic composition, and at least two or more internal electrodes sandwiching the dielectric ceramic layer, The dielectric ceramic composition comprises 100 parts by weight of a basic component;
It consists of a mixture of 0.01 to 3 parts by weight of additive component 1 represented by Me*O* and 0.2 to 5 parts by weight of additive component 2, and the basic component is (Bak-( x*yl MIILyloll fT1+
-JilOa-xzi (where M is Mg and/or Zn
, L is Ca and/or Sr, R is Sc, Y, Gd, Dy
.

One or more metal elements selected from Ho, Er and Yb, k, x, y, z are 1°00≦k≦1.05 0<x<0.10 o<y≦0.05 0.01≦x+y≦0.10 0.002≦z≦0.06), the additive component 1 is composed of CrgOs and/or Al2O, and the additive component 2 is L i z O and S f O2 and MO
(However, MO is BaO, SrO, CaO, MgO and Z
one or more metal oxides selected from nO)
In the triangular diagram showing these compositions in mol%, the composition range of Li5O, 5iO-, and MO is 1 mol% for Li20, 80 mol% for Sing, and 80 mol% for MO. The first point A has a composition of 19 mol%, the L x 20 is 1 mol %, and the S i O2 is 39 mol %.
mol %, a second point B where the MO has a composition of 60 mol %
and a third point C showing a composition of 30 mol% of Li2O, 30 mol% of S i Oa, and 40 mol% of MO; a fourth dot having a composition of 50 mol%, the MO being 0 mol%, and a fourth dot having a composition of 20 mol% the Li*O, 80 mol% the Si'Ot, and 0 mol% the MO. This is within an area surrounded by five straight lines connecting point E of No. 5 in this order.

Here, the value of k is 1. The range of OO≦k≦1.05 is preferable; when the value of is less than 1.00, the resistivity ρ is 1×10
'becomes smaller than MΩ・CI, temperature change rate of capacitance Δ
C-□, 8 CI2% deviates from 115% to +15%, Δ
If C-as and ΔCss deviate from -10% to +10% and the value of k exceeds 1.05, it will not be possible to obtain an m-dense sintered body, but if the value of k is 1.00≦k≦ This is because within the range of 1.05, a dense sintered body having desired electrical characteristics can be obtained.

Further, the value of X+y is preferably in the range of 0.01≦x+y≦0, lO. When the value of x+y is less than 0.01, the temperature change rate ΔC-55 of capacitance deviates from -15% to +15%,
If the value of
This is because when the directivity of x+y is in the range of 0.01≦x+y≦0.10, a product having desired electrical characteristics can be obtained.

However, even if x+y≦0.10, y≦0.05 is preferable. This is because even if x+y≦0.10 is satisfied, if the value of y exceeds 0.05, the capacitance temperature change 8th Css will deviate from 110% to +10%.

In addition, Mg and Zn of the M component and Ca and Sr of the L component work in the same way as f, and Mg and Zn in the range satisfying 2O<x<0.10.
and Zn or both;
One or both of Ca and Sr can be used within a range that satisfies <y≦0.05.

In addition, the value of Z is preferably in the range of 0.002≦z≦0.06. If the value of Z is less than 0.002, the temperature change rate of capacitance ΔC-□ will deviate from -15% to +15%. , ΔC-
If as deviates from -10% to +10% and the value of Z exceeds 0.06, a dense sintered body cannot be obtained, but in the range of 0.002≦z≦0.06, the desired This is because a dense sintered body having the following electrical properties can be obtained.

Note that the R components Sc, Y, Gd, Dy, and Ho.

Er and Yb work in the same way as S, and the same effect can be obtained even if one selected from them is used or a plurality of them are used in combination. Therefore, the value of 2 is desirably within the range of 0.002≦z≦0.06, regardless of whether there is one type of R component or multiple types of R components.

Furthermore, the R component contributes to improving the temperature characteristics of capacitance. That is, by adding the R component, the temperature
Temperature change rate of capacitance △C-1s in the range of ~125℃
~8Cl28 can be easily kept in the range of -15% to +15%, and the temperature change rate of capacitance ΔC-25 to ΔC65 in the range of -25°C to 85°C can be reduced to -10%.
This makes it possible to easily keep the capacitance within the range of ~+10%, and to reduce the fluctuation range of the temperature change rate of capacitance in each temperature range.

Moreover, the R component has the effect of increasing the resistivity ρ and the effect of increasing the sinterability.

In addition, in the above composition formula showing the basic components, X+ y
+ Zr k of course indicates the number of atoms of each element.

In addition, a trace amount of MnOz (preferably 0.05 to 0.000.
A mineralizing agent such as 1% by weight) may be added to improve sinterability. Further, other substances may be added as necessary.

In addition, starting materials for obtaining the basic components may be other than those shown in Examples, such as Bao, SrO.

It may also be an oxide or hydroxide such as CaO or other compounds.

Next, the amount of additive component 1 added is preferably in the range of 0.01 to 3 parts by weight per 100 parts by weight of the basic component. ．．
If it is less than 01, the temperature change rate of capacitance Δc 41i
If it is outside the range of -15% to +15% and exceeds 3.0 parts by weight, a dense sintered body cannot be obtained even if fired at 1250°C, but if the additive component 1 is 0.01 to 3 parts by weight This is because a sintered body having desired characteristics can be obtained when the amount is within the range of .

Note that Cr*Os of the additive component l and A1. O, works in the same way as S, and the same result can be obtained even if one selected from them or a plurality of them are used. And, regardless of whether the additive component 1 is one type or multiple types,
The amount added is 0. It is desirable to set it in the range of O1 to 3.0.

Note that this additive component technique contributes to improving the temperature characteristics of capacitance. That is, the temperature change rate of capacitance due to addition of additive component 1 is ΔC-55 to ΔC1□.

It becomes possible to keep the capacitance temperature change rate ΔC-2, to ΔCas within the range of -15% to +15%, and it becomes possible to easily keep the capacitance temperature change rate ΔC-2, ~ΔCas within the range of -10% to +10%. In addition, the fluctuation width of the temperature change rate of capacitance in each temperature range can be reduced. Further, the additive component 1 has the effect of slightly increasing the resistivity p.

Next, the amount of additive component 2 added is preferably in the range of 0.2 to 5 parts by weight per 100 parts by weight of the basic component. If the amount of additive component 2 added is less than 2 parts by weight of Cl, a dense sintered body cannot be obtained even if the firing temperature is 1250°C, and the amount of additive component 2 exceeds 5 parts by weight. , the relative permittivity ε is less than 3000, and the capacitance temperature change No. 8 C-5s is outside of -15% to +15%, but the additive component 2 is in the range of 0.2 to 5 parts by weight. This is because, in this case, desired electrical characteristics can be obtained.

The composition of additive component 2 is L it OS i OzMO
Preferably, the area is within the area surrounded by five straight lines connecting points 1 to 5 in this order of the triangular diagram showing the composition ratio in mol%.

If the composition of additive component 2 is outside this range, a dense sintered body cannot be obtained, but if the composition is within this range,
This is because a sintered body with desired electrical characteristics can be obtained.

Note that the starting material for additive component 2 may be other compounds such as oxides and hydroxides.

Next, the method for manufacturing a porcelain capacitor according to the present invention includes the steps of preparing a mixture of unsintered porcelain powder consisting of the above-mentioned basic components, additive component 1, and additive component 2; a step of forming a porcelain sheet; a step of forming a laminate in which the unsintered porcelain sheet is sandwiched between at least two conductive paste films; and a step of firing the laminate in a non-oxidizing atmosphere; and a step of heat-treating the fired laminate in an oxidizing atmosphere.

Here, the firing temperature in the non-oxidizing atmosphere can be varied depending on the electrode material.

When using nickel as the internal electrode, 1050'C~1
Almost no aggregation of nickel particles occurs in the 200°C range.

Further, the non-oxidizing atmosphere may be not only a reducing atmosphere such as N2 or co, but also a neutral atmosphere such as N2 or Ar.

Furthermore, the temperature of the heat treatment in the oxidizing atmosphere can be varied in consideration of the electrode material such as nickel and the oxidation of the ceramic.

The temperature of this heat treatment was 600'C in the example, but
The temperature is not limited to this, and the temperature may be lower than the sintering temperature (preferably in the range of 500°C to 1000°C).

Note that the present invention is of course applicable to general single-layer ceramic capacitors other than multilayer ceramic capacitors.

[Example] First, the preparation method of sample No. 1 in Table 1 and its electrical characteristics will be explained.

Motobe yo scolding blade Weigh each compound of Formulation 1, these at 3pm A raw material mixture was obtained by intermittent mixing.

here, Weight of compound of formulation 1 (g) and mole part teeth, General formula of basic components %formula% (11 This is the value calculated so that.

next.

This raw material mixture was dried at 150° C. for 4 hours, pulverized, and calcined in the air at a temperature of about 1200° C. for 2 hours to obtain a powder of the basic component.

Preparation of Addition Formation 2' Also, the compounds of Formulation 2 were each weighed and mixed, 300 cc of alcohol was added to this mixture, and after stirring for 10 hours using an alumina ball in a polyethylene pot, the mixture was heated to 1000°C in the atmosphere. Temporary firing was carried out at the same temperature for 2 hours.

Here, the weight (g) and molar parts of the compound of formulation 2 are L
i z O is 1 mol%, SiO□ is 80 mol%, MO is 19 mol% (BaO (3,8 mol%) + CaO (3,8 mol%)
This value was calculated so that the composition would be (mol%) + SrO (3.8 mol%) + MgO (3.8 mol%) + ZnO (3.8 mol%)).

Next, the material obtained by this calcining was placed in an alumina pot with 300 cc of water, and an alumina ball was used to
Grind for hours, then dry at 150°C for 4 hours,
A powder of additive component 2 was obtained.

Incidentally, the contents of MO are BaO and Cab.

As shown in Table 1, the proportions of SrO, MgO and ZnO are all 20 mol%.

L1 Unit Stand 11 Next, 2 parts by weight (20 g) of the additive component 2 was added to 100 parts by weight (1000 g) of the basic component, and further, the particles were well-aligned with an average particle size of 0.5 μm. Purity 99.
0.1 weight f as an additive component with 0% or more Cr2O*
fi (Ig) was added, and further, an organic binder consisting of an aqueous solution of acrylic ester polymer, glycerin, and condensed phosphate was added in an amount of 15% by weight based on the total weight of the basic component and additive components 1 and 2, and further, Add 50% water by weight,
These were placed in a ball mill, pulverized and mixed to prepare a slurry of porcelain raw materials.

After forming the unmagnetized sheet, the slurry is placed in a vacuum defoaming machine to be defoamed, this slurry is placed in a reverse roll coater, and the thin film molding obtained from this is continuously coated on a long polyester film. The receiver was removed and dried on the same film by heating at 100° C. to obtain an unsintered porcelain sheet with a thickness of about 25 μm.

This sheet is long and is used by cutting it into 10 cm squares.

On the other hand, the conductive paste for internal electrodes has an average particle size of 1.5
10g of μm nickel powder and 0.9g of ethyl cellulose
g dissolved in 9.1 g of butylcarpitol were placed in a stirrer and stirred for 10 hours. Then, this conductive paste was printed on one side of the unsintered porcelain sheet through a screen having 50 patterns of 14 mm in length and 7 mm in width, and then dried.

Layers of Magnetic Sheets 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. Further, four unsintered porcelain sheets each having a thickness of 60 μm were laminated on the upper and lower surfaces of this laminate.

This laminate is then heated at a temperature of about 50°C in the thickness direction for about 40 minutes.
A load of 0 tons was applied to bond the parts.

Thereafter, this laminate was cut into a grid shape to obtain 50 laminate chips.

Next to the chip, this stacked chip is placed in a furnace capable of atmosphere firing.1. 600 at a rate of 100°C/h in an air atmosphere
The organic binder was burned by increasing the temperature to ℃.

After that, the atmosphere of the furnace was changed from the atmosphere to H2 (2% by volume) + N.
, (98% by volume). Then, while maintaining the furnace in this reducing atmosphere, the heating temperature of the stacked chips was increased from 600°C to the sintering temperature of 1150°C.
Raise the temperature at a rate of 100°C/h to 1150°C (maximum temperature)
After holding for 3 hours, the temperature was lowered to 600°C at a rate of 100°C/h, the atmosphere was changed to an air atmosphere (oxidizing atmosphere), and 600°C was held for 30 minutes to perform oxidation treatment.
Thereafter, it was cooled to room temperature to obtain a laminated sintered body chip.

Next, zinc, glass frit, and vehicle (
A conductive paste consisting of a vehicle) was applied and dried, and this was baked in the air at a temperature of 550°C for 15 minutes to form a zinc electrode layer, and then a copper layer was further formed on this using an electroless plating method. , and then on top of this, Pb-
A 3N solder layer was provided to form a pair of external electrodes.

As a result, as shown in FIG. 1, a multilayer ceramic capacitor 10 is obtained in which a pair of external electrodes 16 are formed on a multilayer sintered chip 15 consisting of three dielectric ceramic layers 12 and two internal electrodes 14. It was done.

Here, the external electrode 16 includes a zinc electrode layer 18, a copper layer 20 formed on the zinc electrode layer 18, and a copper layer 20 formed on the zinc electrode layer 18.
and a Pb-3n solder layer 22 formed on top of the Pb-3n solder layer 22.

Note that the dielectric ceramic layer 12 of this multilayer ceramic capacitor 10
The thickness of the dielectric ceramic layer 12 is 0.02 mm, and the opposing area of the pair of internal electrodes 14 is 5 mm x 5 mm = 25 mm.The composition of the dielectric ceramic layer 12 after sintering is a mixture of the basic components and additive components before sintering. The composition is substantially the same.

・, 1 Next, the electrical characteristics of the multilayer ceramic capacitor 10 are measured,
When the average values were calculated, as shown in Table 2, the dielectric constant ε1 was 3710, tan δ was 1.2%, and resistivity ρ was 4.8xlO'MΩ'cm.

-55℃ and +125℃ based on capacitance at 25℃
8th change in capacitance of C1,s to S is -10,9%
, +5.8%, -25°C based on capacitance at 20°C
, rate of change in capacitance at +85°C ΔC-0. Eight Css-
6.1%.

-4.5%.

Note that the electrical characteristics were measured in the following manner.

The IAI dielectric constant ε1 is at a temperature of 20°C, a frequency of 1kHz,
Voltage (effective value) 1. The capacitance was measured under OV conditions, and the measured value and the opposing area of the pair of internal electrodes 14, 25 m
m'' and the thickness of the dielectric ceramic layer 12 between the pair of internal electrodes 14 of 0.02 mm.

(Bl dielectric loss tan δ (%) was measured under the same conditions as the above measurement of relative dielectric constant.

(C1 resistivity p (MO cm) was calculated by measuring the resistance value between a pair of external electrodes 16 after applying DClooV for 1 minute at a temperature of 20'C and based on this measurement value and dimensions. .

(D) Temperature characteristics of capacitance: -55°C, -25°C, 0°C, +20'C by placing the sample in a constant temperature bath.

+25℃, +40℃, +60℃, +85℃.

Frequency 1 at each temperature of +105℃ and +125℃
kHz, voltage (effective value) 1. The capacitance was measured under OV conditions, and the rate of change at each temperature with respect to the capacitance at 20°C and 25°C was obtained.

The preparation method of sample No. 1 and its characteristics have been described above, but for sample No. 2 to 105, the composition of the basic component and additive component 1.2, their ratio, and firing in a reducing atmosphere are also explained. Except for changing the temperature as shown in Tables 1 and 2, multilayer ceramic capacitors were prepared in exactly the same manner as for samples No. 1 and their electrical characteristics were measured in the same manner.

Table 1 shows the composition of the basic components and additive components 1.2 of each sample, and Table 2 shows the firing temperature and electrical characteristics of each sample.

Note that x, y, and z in the basic component column of Table 1 are the number of atoms of each element in the basic component composition formula (1) described above, that is, when the number of atoms of (Ti + R) is 1. Shows the ratio of the number of atoms of each element.

Furthermore, Mg and Zn in the X column indicate the contents of M in the basic component composition formula (1) described above, and Ca + S r in the y column.
indicates the contents of the basic component composition formula (1), and Sc, Y, Gd, Dy in the Z column.

Ho, Er, and Yb are represented by the above-mentioned basic component composition formula (1
) shows the contents of R.

These columns show the number of these atoms, and the total column shows the total value (x+y) of Mg, Zn, Ca, and Sr.

The amounts of additive components 1 and 2 are shown in parts by weight based on 100 parts by weight of the basic component. The MO content column for additive component 2 contains BaO, MgO, and ZnO.

The proportions of SrO and CaO are shown in mol%.

In Table 2, the temperature characteristics of capacitance are as follows: The capacitance change rate at -55℃ and +125℃ based on the capacitance at 25℃ is ΔC-**C%) and ΔC1□ (%). , 20
The capacitance change rates at -25°C and +85°C based on the capacitance at °C are shown as ΔC-1s and ΔC1l@.

Table 2 (1) Samples with X magnetic force 9 dimensions are fi example 1 Table 2 (2) Samples marked with an X are comparative examples Table 2 (3) Samples marked with an X are above] 4 Column Table 2 (4) Samples marked with an X and t fin Table 2 (5) X magnetic force 9 dimensions are ltJ! As is clear from the J+ INI Table and Table 2, the samples according to the present invention have a dielectric constant ε of 3000 or more and a tan δ of 2 when fired at 1200°C or lower in a non-oxidizing atmosphere.
, 5% or less, resistivity ρ is 1X10@MΩ・cm or more, temperature change rate of capacitance ΔC-55 and ΔC125 is 115
% ~ +15%, ΔC-2, and ΔCas -10% ~ +
10%, which makes it possible to obtain a ceramic capacitor with desired characteristics.

On the other hand, sample No. 11-16.26.31°32.40
~44,50,54,55,60°61.67.68.
74.85-87.96-98.104,105 cannot achieve the object of the present invention. Therefore, these are outside the scope of the present invention.

Table 2 shows the temperature change rate of capacitance ΔC-5s+ΔC+t
Although only s+ ΔC-21+ ΔC0 is shown, the temperature change rate ΔC of various capacitances in the range of 25°C to +85°C is -10% to +10% for samples belonging to the scope of the present invention.
%, and the rate of change of various capacitances ΔC in the range of -55°C to +125°C is -15% to +15%.
is within the range.

Next, the reasons for limiting the composition range of the dielectric ceramic composition of the present invention will be described.

First, when the value of x+y is zero as shown in sample No. 32, the temperature change rate of capacitance ΔC-5s is -15
Although it is outside the range of % to +15%, sample No. 33 to 35
As shown in the figure, when the value of X+y is 0.01, desired electrical characteristics can be obtained. Therefore, the lower limit of x+y is 0.
It is 01.

On the other hand, as shown in sample Nos. 41 to 43, when the value of X+3' is 0.12, the capacitance temperature change rate ΔCa
Although s is outside the range of -10% to +io%, sample No.
As shown in 39.49, when the value of x+y is 0.10, desired electrical characteristics can be obtained.

However, as shown in sample No. 40.44, even if the value of x+y is 0.10, if the value of y exceeds 0.05, ΔCss will be in the range of -Ic) to +10%. Therefore, the upper limit of X+3/ is 0.10, but at the same time the upper limit of y must be 0.05.

In addition, Mg and Zn of the M component and Ca and Sr of the L component work in the same way as f, and Mg and Zn in the range satisfying 2O<x<0.10.
and Zn or both, and o
One or both of Ca and Sr can be used within a range that satisfies <y≦0.05. It is desirable that the value of X+y be in the range of 0.01 to 0.10 in either case of one or more of the M component and the L component.

When the value of k is 0.98 as shown in sample No. 50, ρ is significantly low (less than 1×10"MΩ'cm), and the temperature change rate of capacitance is ΔC-5s+ Δc- 2B is also significantly worse than -15% and -10%, respectively, but as shown in sample No. 51, when the value of k is 1.00, the desired electrical characteristics can be obtained. , k has a lower limit of 1.00.

On the other hand, the value of k is 1.0 as shown in sample No. 54.
In the case of sample No. 7, a dense sintered body cannot be obtained, but in the case of sample No.
As shown in 53, when the value of k is 1.05, desired electrical characteristics can be obtained. Therefore, the upper limit of the value of k is 1.0
It is 5.

The value of 2 is 2 sample No. 2 as shown in 55.61.68.
In the case of O, the temperature change rate of capacitance △C-1s, ΔC-
Although aS is not within -15% and -10%, respectively, when the value of 2 is 0.002 as shown in sample No. 56°62.69, desired electrical characteristics can be obtained. Therefore, the lower limit of Z is 0.002.

On the other hand, the value of Z is sample No. 60.67.74°85.8
As shown in Sample No. 6, when the temperature is 0.07, a dense sintered body cannot be obtained even if fired at 1250°C.
As shown in 66.73, 83.84, when the value is 0.06, desired electrical characteristics can be obtained. Therefore, the upper limit of the value of Z is 0.06.

Direction, R component Sc, Y, Gd, Dy, Ho.

Er and Yb work in the same way as f, and the same result can be obtained even if one selected from them is used or a plurality of them are used in combination.

In any case where there is one type of R component or multiple types of R components, it is desirable that the value of Z is in the range of 0.002 to 0.06.

Note that the component represented by R in the compositional formula contributes to improving the temperature characteristics of capacitance. That is, by adding the R component, it becomes possible to easily keep the temperature change rate of capacitance ΔC-5, ~ΔC128 in the range of -55°C to 125°C within the range of -15% to +15%. -25℃～
Temperature change rate of capacitance ΔC-0 to ΔC in the range of 85℃
115 can be easily kept within the range of -10% to +lO%, and the fluctuation width of the temperature change rate of capacitance in each temperature range can be reduced.

Moreover, the R component has the effect of increasing the resistivity ρ and the effect of increasing the sinterability.

Cr2O3 which is additive component 1 and/or A1. ．． 03(
7) When the amount of force n is zero as shown in samples No. 87 and 98, ΔC-5 is less than 115%, but as shown in sample No. 88.89, 99.100. When the amount added is 0.01 part by weight per 100 parts by weight of the basic component, desired characteristics can be obtained. Therefore, the lower limit of additive component 1 is 0.01.

On the other hand, as shown in sample No. 96.97, 104, and 105, when the amount of additive component 1 added is more than 3.0 parts by weight, a dense sintered body cannot be obtained even if fired at 1250°C. However, as shown in sample No. 93-95.103, 3
．． In the case of 0 parts by weight, desired characteristics can be obtained.

Therefore, the upper limit of additive component 1 is 3. This is the OM quantity part.

Note that Cr20x and A L t Os, which are additive components 1, work in the same manner as above, and the same result can be obtained even if one selected from them is used or a plurality of them are used.

In any case where the additive component l is one type or multiple types, it is desirable that the amount added is in the range of o, oi to 3.0.

Note that this additive component 1 contributes to improving the temperature characteristics of capacitance. That is, by adding additive component 1, the temperature
Temperature change rate of capacitance ΔC-55 in the range of 125℃
It becomes possible to keep ΔCl2s in the range of -15% to +15%, and the temperature change rate of capacitance in the range of -25°C to 85°C and Cas to -10% to +10%.
%, and it is possible to reduce the fluctuation width of the temperature change rate of capacitance in each temperature range. Further, the additive component 1 has the effect of slightly increasing the resistivity ρ.

In addition, when the amount of additive component 2 added is zero, sample No.
As is clear from Sample No. 26, even if the firing temperature is 1250°C, a dense sintered body cannot be obtained. However, as shown in Sample No. 27, the addition amount is 0.
．． In the case of 2 parts by weight, desired electrical properties can be obtained by firing at 1190°C. Therefore, the lower limit of additive component 2 is Cl
2 parts by weight.

On the other hand, as shown in sample No. 31, when the amount of additive component 2 is 7.0 parts by weight, the he dielectric constant ε is 300
becomes less than 0, and furthermore, the temperature change of capacitance is
Sample No. 3 is outside the range of -15% to +15%.
As shown in 0, when the amount added is 5.0 parts by weight, desired electrical characteristics can be obtained. Therefore, the upper limit of the amount added is 5.0 parts.

A preferred composition of additive component 2 is Li-0-0- in FIG.
It can be determined based on a triangular diagram showing the composition ratio of 5iO2-.

The first point A in the triangular diagram is that L 120 of sample N091 is 1.
mol%, S i O2 80 mol%, MO 19 mol%
The second point B is Li2O of sample qNo.2.
is 1 mol%, 5iOz is 39 mol%, MO is 60 mol%
The third point C is L x of sample No. 3.
x O is 30 mol%, 5i02 is 30 mol%, MO is 4
It shows a composition of 0 mol%, and the fourth spot is L of sample N094.
1□0 is 50 mol%, SiO2 is 50 mol%, MO is 0
The fifth point E shows the composition of sample FINo. 5 of 20 mol % of Li2O, 80 mol % of 5iO-, and 0 mol % of MO.

The composition of additive component 2 of the sample that falls within the scope of the present invention is within the region surrounded by five straight lines connecting points 1 to 5 of the triangular diagram in order. If the composition is within this range, desired electrical characteristics can be obtained.

On the other hand, if the composition of additive component 2 falls outside the range specified in the present invention, as in Sample Nos. 11 to 16, a dense sintered body cannot be obtained.

Incidentally, the MO acid components include, for example, BaO, MgO, and ZnO as shown in Sample Nos. 21 to 25.

It may be either one of SrO or CaO, or it may be in an appropriate ratio as shown in other samples.

[Effects of the Invention] According to the present invention, since the composition of the dielectric ceramic composition is as described above, the dielectric constant is 3000 or more, and the dielectric loss t is
anδ is 2.5% or less, resistivity ρ is lX10'MΩ・c
m or more, and the temperature change rate of the relative permittivity is -55°C
-15% to +15% at ~125℃ (based on 25℃), -
-10% to +10% at 25℃ to 85℃ (based on 20℃)
It is possible to provide a ceramic capacitor with a dielectric ceramic composition falling within the range of .

Further, according to the present invention, in a non-oxidizing atmosphere, 12
Since it can be obtained by firing at a temperature of 00°C or less, it is 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 at the same time. can.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing a multilayer ceramic capacitor according to an embodiment of the present invention, and FIG. 2 is a triangular diagram showing the composition range of additive component 2. 2...-Porcelain layer, 4... Internal electrode, 6... External electrode.

Claims (1)

[Claims] 1. A ceramic capacitor comprising a dielectric ceramic layer made of a dielectric ceramic composition and at least two or more internal electrodes sandwiching the dielectric ceramic layer, wherein the dielectric ceramic composition contains 100 parts by weight of the basic ingredients and
It consists of a mixture of 0.01 to 3 parts by weight of additive component 1 represented by Me_2O_3 and 0.2 to 5 parts by weight of additive component 2, and the basic component is (Ba_k_-_(_x_+_y_)M_xL_y )O
＿k(Ti_1_-_zR_z)O_2_-_z_/_
2 (However, M is Mg and/or Zn, L is Ca and/or Sr, R is Sc, Y, Gd, Dy, Ho, Er, and Y
one or more metal elements selected from b, k,
x, y, z satisfy 1.00≦k≦1.05 0<x<0.10 0<y≦0.05 0.01≦x+y≦0.10 0.002≦z≦0.06 The additive component 1 is composed of Cr_2O_3 and/or Al_2O_3, and the additive component 2 is Li_2O, SiO_2, and MO (provided that MO is selected from BaO, SrO, CaO, MgO, and ZnO). The composition range of the Li_2O, the SiO_2, and the MO is in a triangular diagram showing these compositions in mol%, the Li_2O is 1 mol%, the SiO_2 is A first point A having a composition of 80 mol% of Li_2O, 19 mol% of the MO, and a second point A having a composition of 1 mol% of the Li_2O, 39 mol% of the SiO_2, and 60 mol% of the MO. B; a third point C having a composition of 30 mol% of Li_2O, 30 mol% of SiO_2, and 40 mol% of MO; 50 mol% of Li_2O, 50 mol% of SiO_2, and 40 mol% of MO; A fourth point D showing a composition of 0 mol% of Li_2O, a fifth point E showing a composition of 20 mol% of Li_2O, 80 mol% of SiO_2, and 0 mol% of MO are connected in this order 5 A porcelain capacitor characterized by being located within the area bounded by the straight line of the book. 2. A step of preparing a mixture made of unsintered porcelain powder, a step of forming an unsintered porcelain sheet made of the mixture, and a lamination in which the unsintered porcelain sheet is sandwiched between at least two or more conductive paste films. forming a product, firing the laminate in a non-oxidizing atmosphere, and heat-treating the fired laminate in an oxidizing atmosphere, from the unsintered porcelain powder. A mixture consisting of 100 parts by weight of the basic component and 0.01 to 3 parts by weight of Me
It consists of additive component 1 represented by _2O_3 and 0.2 to 5 parts by weight of additive component 2, and the basic component is (Ba_k_-_(_x_+_y_)M_xL_y)O
＿k(Ti_1_-_zR_z)O_2_-_z_/_
2 (However, M is Mg and/or Zn, L is Ca and/or Sr, R is Sc, Y, Gd, Dy, Ho, Er, and Y
one or more metal elements selected from b, k,
x, y, and z satisfy 1.00≦k≦1.05 0<x<0.10 0<y≦0.05 0.01≦x+y≦0.10 0.002≦z≦0.06 The additive component 1 is composed of Cr_2O_3 and/or Al_2O_3, and the additive component 2 is Li_2O, SiO_2, and MO (provided that MO is selected from BaO, SrO, CaO, MgO, and ZnO). The composition range of the Li_2O, the SiO_2, and the MO is in a triangular diagram showing these compositions in mol%, the Li_2O is 1 mol%, the SiO_2 is A first point A having a composition of 80 mol% of Li_2O, 19 mol% of the MO, and a second point A having a composition of 1 mol% of the Li_2O, 39 mol% of the SiO_2, and 60 mol% of the MO. B; a third point C having a composition of 30 mol% of Li_2O, 30 mol% of SiO_2, and 40 mol% of MO; 50 mol% of Li_2O, 50 mol% of SiO_2, and 40 mol% of MO; A fourth point D showing a composition of 0 mol% of Li_2O, a fifth point E showing a composition of 20 mol% of Li_2O, 80 mol% of SiO_2, and 0 mol% of MO are connected in this order 5 A method for manufacturing a ceramic capacitor, characterized in that the capacitor is located within an area surrounded by straight lines of a book.