JP2001080959A - Dielectric ceramic composition and laminated ceramic parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a ceramic having high dielectric constant and Q value, almost free form fluctuation of the characteristics and capable of being sintered at a low temperature by incorporating, as a first sub-component, SiO2 glass free from a Pb oxide in a specific ratio and, as a second sub-component, an Mn oxide in a specified ratio into a particular main component. SOLUTION: This composition is expressed by the formula x(BaαCaβ Srγ)O- y[TiO2)1-m(ZrO2)m]-zRe2O3 (wherein, x+y+z=100; α+β+γ=1; 0<=β+γ<0.8; 0<=m<0.15; and Re is at least one rare earth element). The content (a) of the first sub-component is >=0.1 and <=25 pts.wt. and the content (b) of the second sub-component is >1.5 and <=20 pts.wt. expressed in terms of MnO, each content being based on 100 pts.wt. of the main component whose molar composition ratio (BaαCaβSrγ)O, [(TiO2)1-m(ZrO2)m], Re2O3} of (BaαCaβSrγ)O, [(TiO2)1-m] and Re2O3 is contained in a region surrounded by points A (7, 85, 8), B (7, 59, 34), C (0, 59, 41) and D (0, 85, 15).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dielectric ceramic composition for temperature compensation and a multilayer ceramic component using the same, such as a multilayer ceramic capacitor or a multilayer LC filter.

[0002]

2. Description of the Related Art Conventionally, ceramic capacitors for temperature compensation have been widely used for tuning, resonance and the like in various electronic devices, and there has been a demand for a capacitor having a small size, a small dielectric loss and a stable dielectric characteristic. . For this purpose, the dielectric ceramic is required to have a large relative dielectric constant and a small dielectric loss in response to a demand for miniaturization (that is, a small dielectric loss).
Q value is large).

As such a dielectric ceramic, Ba is used.
O-TiO ₂ based dielectric ceramic compositions have been proposed [H. M. O'Brayan, J .; Am. Cera
m. Soc. , 57 (1974) 450;
20905, etc.]. Multilayer ceramic capacitors using these dielectric ceramic compositions have been put to practical use. However, since the firing temperature is as high as 1300 ° C. to 1400 ° C., palladium (P
d) or platinum (Pt) must be used.

However, in recent years, BaO—TiO ₂ —Nd ₂ O _{3 has been} used as a dielectric ceramic composition that can be fired at a low temperature.
The main component of the system _{PbO-ZnO-B 2 O 3} -Al 2 O 3 -Si
Dielectric ceramic compositions to which O ₂ -based glass is added (JP-A-5-234420), BaO-TiO _2-
Nd ₂ O ₃ based main component _{PbO-V 2 O 5 -B 2} O 3 -SiO of
Dielectric ceramic compositions (Japanese Patent Application Laid-Open No. 8-239262) to which a _two- system glass is added, BaO-TiO ₂ -N
d ₂ O ₃ -Sm ₂ O ₃ based PbO-ZnO-B ₂ O ₃ as a main component of
A dielectric ceramic composition to which glass having a softening point of 500 ° C. or lower such as a system is added (Japanese Patent Application Laid-Open No. 9-71462) has been proposed.

[0005]

However, Japanese Patent Application Laid-Open Nos. Hei 5-234420 and Hei 8-23926 describe the above.
In each of the dielectric ceramic compositions disclosed in JP-A No. 2 and JP-A-9-71462, glass containing a Pb oxide component is added for low-temperature sintering.

However, this Pb oxide component has a high volatility at the time of sintering, and the content thereof varies within a lot or between lots at the time of producing a glass or sintering a ceramic. There was a problem that it was easy.

On the other hand, as described in JP-A-9-71462, glass containing no Pb component often has a softening point higher than 500 ° C., which is disadvantageous for low-temperature firing. Had.

Accordingly, an object of the present invention is to provide a dielectric constant and a Q value.
Highly reliable dielectric ceramic composition for temperature compensation having high value, capable of low-temperature sintering, and having little variation in ceramic characteristics due to firing, and multilayer ceramic capacitors and multilayer LC filters using the same. To provide a multilayer ceramic component.

[0009]

[MEANS FOR SOLVING THE PROBLEMS]
According to claim 1, the dielectric ceramic composition of the present invention
The product has the formula x (BaαCaβSrγ) Oy [(Ti
O_Two)_1-m(ZrO_Two)_m ] -ZRe_TwoO_Three(However, in the formula,
x + y + z = 100, α + β + γ = 1, 0 ≦ β + γ <
0.8, 0 ≦ m <0.15, and Re is at least
One or more rare earth elements. ), And these (Baα
CaβSrγ) O and [(TiO_Two)_1-m(ZrO_Two)_m ]
And Re_TwoO_ThreeThe molar composition ratio of ｛(BaαCaβSrγ) O,
[(TiO_Two) _1-m(ZrO_Two)_m ], Re_TwoO_Three｝,
In the ternary composition diagram shown in FIG. 1 attached, the point A (7,85,
8), point B (7, 59, 34), point C (0, 59, 4)
1), within the area surrounded by point D (0, 85, 15) (however,
However, it does not include on the line connecting the points A and B. )
Glass is included as the first subcomponent with respect to 100 parts by weight.
The glass is SiO_TwoSystem glass (however, P
b containing no oxide), and having a content a (parts by weight)
Is 0.1 ≦ a ≦ 25, and as a second subcomponent
Mn oxide is contained, and the content b of the Mn oxide
(Parts by weight) is 0.5 <b ≦ 20 in terms of MnO.
It is characterized by the following.

According to a second aspect of the present invention, in the dielectric ceramic composition of the present invention, the glass as the first subcomponent is a B ₂ O ₃ —SiO ₂ glass (but not containing a Pb oxide. ).

According to a third aspect of the present invention, in addition to the first and second subcomponents, the dielectric ceramic composition of the present invention further comprises Cu as a third subcomponent based on 100 parts by weight of the main component. An oxide is contained, and the content c (parts by weight) of the Cu oxide is c ≦ 10 in terms of CuO.

According to a fourth aspect of the present invention, there is provided a multilayer ceramic component according to the present invention, wherein 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. And an electrode, wherein the dielectric ceramic layer is composed of the dielectric ceramic composition according to any one of claims 1 to 3, and the internal electrode is composed mainly of Cu or Ag. I do.

The rare earth element Re in the present invention is:
La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, T
b, Dy, Ho, Er, Tm, Yb or Lu.

[0014]

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. 2 is a cross-sectional view showing an example of the multilayer ceramic capacitor, and FIG.
FIG. 4 is a plan view showing a dielectric ceramic layer portion having internal electrodes, and FIG. 4 is an exploded perspective view showing a ceramic laminate portion of the multilayer ceramic capacitor of FIG.

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

Next, a method of manufacturing the multilayer ceramic capacitor 1 will be described in the order of manufacturing steps.

First, raw material powders, which are components of the dielectric ceramic layers 2a and 2b and are weighed and mixed at a predetermined ratio, are prepared. That is, a main component of BaO—TiO ₂ —Re ₂ O ₃ system (however, Ba is replaced by Ca or Sr, TiO ₂
Is replaced with ZrO ₂ . ), A SiO ₂ -based or B ₂ O ₃ —SiO ₂ -based glass (but not containing any Pb oxide) as a first subcomponent, and a Mn oxide as a second subcomponent. A raw material powder capable of producing a dielectric ceramic composition is prepared. More preferably, a raw material powder capable of producing a dielectric ceramic composition containing a Cu oxide as a third subcomponent 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.
Green sheets for the dielectric ceramic layers 2a and 2b are obtained. Thereafter, as shown in FIG. 3, an internal electrode 4 containing Cu or Ag as a main component is formed on one main surface of the green sheet to be the dielectric ceramic layer 2b. The method for forming the internal electrodes 4 may be either screen printing or the like, or may be deposition or plating.

Next, as shown in FIG. 4, after laminating a required number of green sheets for the dielectric ceramic layer 2b having the internal electrodes 4, each green sheet for the dielectric ceramic layer 2a having no internal electrodes is formed. The sheet is sandwiched between the sheets and pressed to form a green sheet laminate. Thereafter, the laminate is fired at a predetermined temperature to obtain a ceramic laminate 3 shown in FIG.

Next, external electrodes 5 are formed on both end surfaces of the obtained 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 that of the internal electrode 4 can be used, and for example, a silver-palladium alloy or the like can be used. In addition, B ₂ O ₃ —SiO ₂ —BaO-based glass, Li ₂
Although a glass frit such as an O—SiO ₂ —BaO-based glass is also used, an appropriate material is selected in consideration of the use and place of use 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, but depending on an electrode material to be used, a green sheet laminate is formed before firing. It may be applied and formed simultaneously with the ceramic laminate 3.

Next, the surface of the external electrode 5 is plated with nickel, copper, or the like to form a first plating layer 6, and finally, on the first plating layer 6, solder, tin, or the like is formed. No.
2 is formed, and the multilayer ceramic capacitor 1 is formed.
To complete. It should be noted that forming a conductor layer on the surface of the external electrode 5 by plating or the like may be omitted depending on the use and place of use of the multilayer ceramic capacitor.

As described above, the ceramic composition of the present invention used as the dielectric of the multilayer ceramic capacitor has the following characteristics:
It is possible to fire at a temperature lower than the melting point of u or Ag. The relative permittivity of the obtained ceramic is as high as 30 or more, the Q value is as high as 1000 or more at 1 MHz, and the capacitance temperature coefficient (TCC) is as small as ± 30 ppm / ° C. Also, by placing the glass of the first subcomponent B ₂ O ₃ -SiO ₂ glass (but not including Pb oxide), can facilitate the low-temperature sintering. Furthermore, by including a predetermined amount of Cu oxide as a third subcomponent in the ceramic composition, sintering at a lower temperature can be performed.

[0023]

Next, the present invention will be described more specifically based on examples.

(Example 1) A dielectric ceramic composition of the present invention and a ceramic capacitor using the same were produced as follows.

First, as a starting material, barium carbonate (B
aCO ₃ ), calcium carbonate (CaCO ₃ ), strontium carbonate (SrCO ₃ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), rare earth oxide (Re
₂ O ₃ ), manganese carbonate (MnCO ₃ ), and copper oxide (C
uO) was prepared.

After that, these raw material powders were used in Tables 1 and 2
Each composition shown in the following (however, the glass component as the first subcomponent)
Excluding minutes. ), And weigh with ethanol.
Into a ball mill and wet-mix for 16 hours.
Crushed and calcined at 1040 ° C. to obtain calcined powder. this
The average particle size of the obtained calcined powder was 0.9 μm.
Was. In addition, the content of MnO as the second subcomponent,
The content of CuO as the third subcomponent is the main component.
｛X (BaαCaβSrγ) Oy [(TiO _Two)_1-m
(ZrO_Two)_m ] -ZRe_TwoO_Three｝ (Where x + y
+ Z = 100, α + β + γ = 1, 0 ≦ β + γ <0.8,
0 ≦ m <0.15, and Re is at least one or more
Rare earth elements. ) Shows the number of parts per 100 parts by weight.
In Tables 1 and 2, the sample number was marked with *.
Are outside the scope of the present invention, and the others are within the scope of the present invention.
It is in the box.

[0027]

[Table 1]

[0028]

[Table 2]

Further, as the first subcomponent, glass types A to G and I shown in Table 3 and SiO ₂ or B ₂ O ₃ --Si
An O ₂ -based glass powder (with a coefficient of% by weight) was prepared.

[0030]

[Table 3]

Next, the glass powder and the calcined powder obtained above were weighed at the ratios shown in Tables 1 and 2, and a polyvinyl butyral solution was added and mixed to form a slurry. A green sheet having a thickness of 50 μm was obtained by molding into a sheet by the method. In addition, the content of the glass is represented by the following formula: Δx (BaαCaβSrγ) O-
y [(TiO ₂ ) _1-m (ZrO ₂ ) _m ] -zRe ₂ O ₃ ｝
(Where x + y + z = 100, α + β + γ = 1,
0 ≦ β + γ <0.8, 0 ≦ m <0.15, and Re
Is at least one or more rare earth elements. ) Indicates the number of parts per 100 parts by weight.

Next, a plurality of green sheets are obtained.
(13 pieces) After stacking and crimping, punching out, diameter 1
A molded product having a thickness of 4 mm and a thickness of 0.5 mm was obtained. Then this
N_TwoBinder after heat treatment at 350 ° C in atmosphere
After removing_Two-N_Two-H _TwoReducing atmosphere made of O gas
In an atmosphere, bake for 2 hours at the baking temperature shown in Tables 4 and 5.
Thus, a disk-shaped ceramic was obtained. And the obtained security
A single-layer circle formed by coating In-Ga electrodes on both main surfaces of the lamic
A plate-type ceramic capacitor was used.

[0033]

[Table 4]

[0034]

[Table 5]

Next, the electrical characteristics of these ceramic capacitors were measured. Capacitance and Q are frequency 1 at 20 ° C.
The sample was measured at MHz and a voltage of 1 Vrms, the dimensions of the sample diameter (D) and thickness (T) were measured, and the relative dielectric constant (εr) was calculated from the capacitance. The TCC (capacitance temperature coefficient) was calculated according to the following formula 1 by measuring each capacitance at 20 ° C. and 85 ° C. Here, in the formula, Cap20 represents the capacitance [pF] at 20 ° C., and Cap85 is 8
Indicates the capacitance [pF] at 5 ° C.

[0036]

[Formula 1] Tables 4 and 5 show the above results. In Tables 4 and 5, samples marked with an asterisk (*) are out of the scope of the present invention, and others are within the scope of the present invention.

As is clear from Tables 1 and 4, sample numbers 5 to 7, 9, 10, 16 to 18, 20, 21, 21 and 2
The ceramic having the composition within the scope of claim 1 of the present invention as shown in 5, 27, and 28 has a main component of Δx (BaαCaβSrγ) O
_{-Y [(TiO 2) 1-} m (ZrO 2) m] -zRe 2 O 3}
(Where x + y + z = 100, α + β + γ = 1,
0 ≦ β + γ <0.8, 0 ≦ m <0.15, and Re
Is at least one or more rare earth elements. ), The first
By containing a SiO ₂ -based glass (but not including a Pb oxide) as a subcomponent of Mn oxide and a Mn oxide as a second subcomponent, the dielectric constant is as high as 30 or more, and the Q value is high. At 1 MHz, a dielectric ceramic having a small temperature coefficient of capacitance (TCC) of ± 30 ppm / ° C. or less, and the melting point of Cu (1083 ° C.)
Sinter below 1060 ° C, which is lower.

Further, in such a configuration, as apparent from Sample Nos. 21 and 23 and Sample Nos. 27 and 28, the glass described in claim 2 is a glass of B ₂ O ₃ —SiO ₂ system (however, Pb oxide is not included)
Lower temperature sintering becomes possible.

Further, sample numbers 35 and 36 in Tables 2 and 5
As described in claim 3, the first and second components are
By containing the third sub-component Cu oxide in addition to the sub-component, sintering can be further performed at low temperature. In addition, since the composition does not contain a Pb oxide component that is easily evaporated, fluctuations in ceramic characteristics due to firing are suppressed.

Here, the reason for limiting the composition of the present invention will be described.

As shown in sample numbers 1 to 4 in Tables 1 and 4, the main component Δx (BaαCaβSrγ) Oy [(TiO ₂ )
_1-m (ZrO ₂ ) _m ] -zRe ₂ O ₃ } (where x +
y + z = 100, α + β + γ = 1, 0 ≦ β + γ <0.
8, 0 ≦ m <0.15, and Re is at least one or more rare earth elements. ) Are points A (7, 85, 8) and points B (7, 59, 3) in the ternary composition diagram shown in FIG.
4), point C (0, 59, 41), point D (0, 85, 1)
Outside the region enclosed by 5), the temperature coefficient of capacitance (TCC) is out of the range of ± 30 ppm / ° C., or the sinterability is reduced, and the temperature is lower than 1083 ° C. which is the melting point of Cu.
It does not sinter at 0 ° C., or its Q value deteriorates to less than 1,000. Therefore, the main components are the points in the ternary composition diagram of FIG.
It is preferable to be within an area surrounded by A, B, C, and D (however, it does not include a line connecting points A and B). Specifically, B
When the total content x of a, Ca and Sr is 7 or more, the capacitance temperature coefficient (TCC) is out of the range of ± 30 ppm / ° C. Therefore, it is preferable that 0 ≦ x <7. When the total content y of Ti and Zr is less than 59, the sinterability is reduced, and sintering is not performed at 1060 ° C., which is lower than 1083 ° C., which is the melting point of Cu. It becomes less than 1000. Therefore, it is preferable that 59 ≦ y ≦ 85.

As shown in Sample Nos. 5 to 7, when a part of BaO is replaced with Ca or Sr, there is an effect of increasing the relative dielectric constant. However, as shown in Sample No. 8, the replacement amount of Ca oxide and Sr oxide is increased. If the sum of β and γ is 0.8 or more, the sinterability is reduced, and sintering is not performed at 1060 ° C., which is lower than the melting point of Cu. Therefore, it is preferable that 0 ≦ β + γ <0.8.

Further, when a part of TiO ₂ is replaced by ZrO ₂ , the effect of preventing reduction of the main component composition is obtained, so that simultaneous firing with a Cu conductor or the like can be advantageously achieved in a reducing atmosphere. However, when the substitution amount m of ZrO ₂ is 0.15 or more, as in the sample No. 11, the sinterability is reduced and sintering is not performed at 1060 ° C., which is lower than the melting point of Cu. Therefore,
0 ≦ m <0.15 is preferred.

As shown in sample numbers 16 to 18, the first
Including glass (but not containing Pb oxide) as an auxiliary component of has the effect of improving sinterability, but as shown in sample No. 15, the glass content a (parts by weight) is If it is less than 0.1, the sinterability is reduced, and 1 below the melting point of Cu.
Does not sinter at 060 ° C. On the other hand, like sample number 19,
If the content a exceeds 25, the Q value deteriorates and becomes as low as less than 1,000. Therefore, it is preferable that 0.1 ≦ a ≦ 25.

As shown in Sample Nos. 23 to 25, the second
The inclusion of the Mn oxide, which is a subcomponent of, has the effect of improving sinterability, further reducing the temperature coefficient of capacitance (TCC), and shifting to the plus side. However, when the content b (parts by weight) of Mn oxide converted to MnO is 0.5 or less as in Sample No. 22, the capacitance temperature coefficient (TCC) is out of the range of ± 30 ppm / ° C.
When the content b exceeds 20, as in sample No. 26, the Q value is as low as less than 1,000. Therefore,
0.5 <b ≦ 20 is preferred.

The inclusion of Cu oxide as the third subcomponent has the effect of improving the sinterability.
When the content c (parts by weight) of Cu oxide converted to CuO exceeds 10, as shown in sample No. 37, Q deteriorates and becomes smaller than 1,000. Therefore, c ≦ 10 is preferred.

Example 2 A multilayer ceramic capacitor according to one example of the present invention was manufactured as follows.

That is, first, barium carbonate (BaCO ₃ ), calcium carbonate (CaCO ₃ ),
Strontium carbonate (SrCO ₃ ), titanium oxide (Ti
O ₂ ), zirconium oxide (ZrO ₂ ), rare earth oxide (Re ₂ O ₃ ), manganese carbonate (MnCO ₃ ), and copper oxide (CuO 2) were prepared.

Thereafter, these raw material powders were weighed so as to obtain the composition shown in Sample No. 41 of Table 6 (however, excluding the glass component as the first subcomponent), and placed in a ball mill together with ethanol to obtain a composition. After 10 hours wet mixing
Calcination at ℃ gave a calcined powder. The content of MnO as the second subcomponent and CuO as the third subcomponent were
Of the main component, Δx (BaαCaβSrγ)
Oy [(TiO ₂ ) _{1 -m} (ZrO ₂ ) _m ] -zRe
₂ O ₃ ｝ (where x + y + z = 100, α + β + γ
= 1, 0 ≦ β + γ <0.8, 0 ≦ m <0.15, and Re is at least one or more rare earth elements. ) 10
The number is based on 0 parts by weight. In Table 6, those marked with an asterisk (*) are out of the scope of the present invention.

[0050]

[Table 6]

As a first subcomponent, a glass powder of glass type H shown in Table 3, ie, 15B ₂ O ₃ -85SiO ₂ (the coefficient is% by weight) was prepared.

Next, 10 parts by weight of this glass powder and a polyvinyl butyral solution were added to 100 parts by weight of the calcined powder obtained above and mixed to form a slurry, and the slurry was sheet-formed by a doctor blade method. To obtain a green sheet.

Subsequently, a conductive paste containing Cu as a main component was printed on the green sheet to form a conductive paste layer for forming internal electrodes. Thereafter, a plurality of green sheets on which the conductive paste layer is formed are stacked such that the side from which the conductive paste layer is drawn out is alternated, and further, on both end surfaces of the laminate where the conductive paste layer is exposed. Then, a conductive paste containing Cu as a main component was applied to obtain a laminate.

Then, the laminate was heat-treated at 350 ° C. in an N ₂ atmosphere to remove the binder, and then the H ₂ −
In a reducing atmosphere consisting of N ₂ -H ₂ O gas, 100
This was held at 0 ° C. for 2 hours and fired to obtain a multilayer ceramic capacitor.

The external dimensions of the multilayer ceramic capacitor thus obtained are 1.6 mm in width, 3.2 mm in length and 1.2 mm in thickness, and the thickness of the dielectric ceramic layer interposed between the internal electrodes is 6 μm. The total number of effective dielectric ceramic layers was 150.

As a comparative example, sample No. 42 in Table 6 was used.
A multilayer ceramic capacitor using the composition shown in (1) as a dielectric was produced.

First, as starting materials, barium carbonate (BaCO ₃ ), calcium carbonate (CaCO ₃ ), strontium carbonate (SrCO ₃ ), titanium oxide (Ti
O ₂ ), zirconium oxide (ZrO ₂ ), rare earth oxide (Re ₂ O ₃ ), manganese carbonate (MnCO ₃ ), copper oxide (CuO 2), boron oxide (B ₂ O ₃ ), silicon oxide (Si
O ₂ ) was prepared.

Thereafter, these raw material powders were weighed so as to obtain a composition (except for B ₂ O ₃ and SiO ₂ ) shown in Sample No. 42 of Table 6, placed in a ball mill together with ethanol, and wet-processed for 16 hours. After mixing, the mixture was calcined at 1040 ° C. to obtain a calcined powder. The content of MnO as the second subcomponent and CuO as the third subcomponent is determined by the following formula: {x (BaαCaβSrγ) Oy [(Ti
O ₂ ) _1-m (ZrO ₂ ) _m ] -zRe ₂ O ₃ } (wherein,
x + y + z = 100, α + β + γ = 1, 0 ≦ β + γ <
0.8, 0 ≦ m <0.15, and Re is at least one or more rare earth elements. ) 100 parts by weight.

Next, 1.5 parts by weight of boron oxide (B ₂ O ₃ ), 8.5 parts by weight of silicon oxide (SiO ₂ ), and a polyvinyl butyral solution were added to 100 parts by weight of the calcined powder. In addition, the mixture was mixed to form a slurry, and this slurry was formed into a sheet by a doctor blade method to obtain a green sheet. Thereafter, a multilayer ceramic capacitor was manufactured in the same manner as in Sample No. 41 described above.

Next, the multilayer ceramic capacitors of Sample Nos. 41 and 42 in Table 6 thus obtained were
A moisture resistance load test was performed. That is, a DC voltage of 16 V was continuously applied to the capacitor for 250 hours in an atmosphere at a pressure of 2 atm, a relative humidity of 100%, and a temperature of 121 ° C. Then, if the insulation resistance of the capacitor became 1 × 10 ⁶ Ω or less during that time, it was determined to be failure (defective). Table 7 shows the results. In Table 7, those marked with an asterisk (*) are out of the scope of the present invention.

[0061]

[Table 7]

As is clear from the sample No. 41 in Tables 6 and 7, the multilayer ceramic capacitor of the present invention containing the B component and the Si component as glass has no defect due to a moisture resistance load test and has a good moisture resistance characteristic. Are better. On the other hand, as shown in Sample No. 42, according to the present invention in which the B component and the Si component are contained as boron oxide (B ₂ O ₃ ) and silicon oxide (SiO ₂ ) and the dielectric composition does not contain glass. A capacitor out of the range is defective due to a moisture resistance load test and has poor moisture resistance characteristics. This indicates that the presence of B ₂ O ₃ —SiO ₂ glass is effective in improving the moisture resistance.

In each of the above embodiments, barium carbonate (BaCO ₃ ), calcium carbonate (CaCO ₃ ), strontium carbonate (SrCO ₃ ), titanium oxide (TiO ₂ ),
Zirconium oxide (ZrO ₂ ), rare earth oxide (Re ₂ O
₃ ), manganese carbonate (MnCO ₃ ) and copper oxide (CuO)
Were mixed at once and calcined. However, barium carbonate (BaCO ₃ ), calcium carbonate (CaCO ₃ ),
Strontium carbonate (SrCO ₃ ), titanium oxide (Ti
O ₂ ), zirconium oxide (ZrO ₂ ) and rare earth oxide (Re ₂ O ₃ ) are mixed and calcined to produce manganese carbonate (MnCO ₃ ) and copper oxide (CuO). The effect of is obtained.

As a starting material, barium carbonate (B
aCO ₃ ), calcium carbonate (CaCO ₃ ), strontium carbonate (SrCO ₃ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), rare earth oxide (Re
₂ O ₃ ), manganese carbonate (MnCO ₃ ) and copper oxide (Cu
Although O 2) was used, the invention is not limited to these compound forms. For example, BaTiO ₃ , Ba ₂ T
i ₉ O ₂₀ , Ba ₄ Ti ₁₃ O ₃₀ , BaZrO ₃ , CaTi
O ₃ , CaZrO ₃ , SrTiO ₃ , SrZrO ₃ , Re ₂
Similar properties can be obtained by using a compound such as Ti ₂ O ₇ (where Re indicates a rare earth element), or a carbonate, oxalate, hydroxide, alkoxide, or the like.

Although the calcining temperature was also set at 1040 ° C., the same characteristics can be obtained at 900 to 1049 ° C. Further, the average particle size of the obtained calcined product was 0.9 μm, but was 0.81 to 5.0 μm.
Then, similar characteristics can be obtained.

Further, as the glass, SiO ₂
Configured as a system or B ₂ O ₃ -SiO ₂ -based, long glass containing no Pb oxide, it is not particularly limited.

Further, even in a laminated LC filter or the like composed of a capacitor made of the dielectric ceramic composition according to the present invention, excellent effects can be obtained in the same manner as in the above embodiment.

[0068]

As is clear from the above description, according to the dielectric porcelain composition of the present invention, it sinters at 1060 ° C. or less, has a relative dielectric constant of 30 or more, and has a Q value of 1000 or more at 1 MHz. , And the temperature coefficient of capacitance (TCC) is ± 30p
Various characteristics such as as small as pm / ° C. or less are obtained. And
Since there is no volatilization of the Pb oxide component, it is possible to obtain a dielectric ceramic composition with small variations in characteristics.

Therefore, when this dielectric ceramic composition is used as a dielectric ceramic layer to constitute a multilayer ceramic capacitor, a multilayer LC filter, or the like, excellent moisture resistance can be obtained, and inexpensive Cu or Ag can be used as an electrode material. Therefore, the cost of the multilayer ceramic component can be reduced.

[Brief description of the drawings]

FIG. 1 shows a preferable range of a main component in a composition of the present invention. {(BaαCaβSrγ) O, [(TiO ₂ )
_1-m (ZrO ₂ ) _m ], Re ₂ O ₃ ｝ ternary composition diagram.

FIG. 2 is a sectional view showing a multilayer ceramic capacitor according to an embodiment of the present invention.

FIG. 3 is a plan view showing a dielectric ceramic layer having an internal electrode in the multilayer ceramic capacitor of FIG. 2;

FIG. 4 is an exploded perspective view showing a ceramic laminate portion of the multilayer ceramic capacitor of FIG. 2;

[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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01B 3/12 311 H01B 3/12 311 326 326 H01G 4/12 358 H01G 4/12 358 4/30 301 4 / 30 301E F-term (reference) 4G031 AA04 AA05 AA06 AA07 AA11 AA12 AA19 AA25 AA28 AA30 AA39 BA09 CA03 5E001 AB03 AC04 AC09 AE00 AE01 AE02 AE03 AE04 AF00 AF06 AH01 AH05 AH09 AJ01 AJ02 EB03 AE04 FG27 FG54 GG10 GG11 GG26 GG28 JJ03 JJ05 JJ12 JJ21 JJ23 LL02 MM22 MM24 PP03 5G303 AA01 AB06 AB08 AB11 AB15 BA12 CA03 CB02 CB03 CB06 CB11 CB15 CB18 CB22 CB26 CB30 CB39 CB35 CB35 CB35 CB35 CB35 CB35 CB35 CB35

Claims (4)

[Claims] 1. The formula x (BaαCaβSrγ) Oy
[(TiO_Two)_1-m(ZrO_Two)_m ] -ZRe_TwoO_Three(However
Where x + y + z = 100, α + β + γ = 1, 0 ≦
β + γ <0.8, 0 ≦ m <0.15, and Re is small
At least one rare earth element. ) And this
(BaαCaβSrγ) O and [(TiO_Two) _1-m(Zr
O_Two)_m ] And Re_TwoO_ThreeMolar ratio of (BaαCaβS
rγ) O, [(TiO_Two)_1-m(ZrO_Two)_m ], Re_TwoO
_Three｝ Indicates a point A in the ternary composition diagram shown in FIG.
(7, 85, 8), point B (7, 59, 34), point C
(0,59,41), surrounded by point D (0,85,15)
(However, it does not include on the line connecting point A and point B.)
Contains glass as a first subcomponent with respect to 100 parts by weight of the main component in
SiO_TwoGlass (but not containing Pb oxide)
Therefore, the content a (parts by weight) is 0.1 ≦ a ≦ 25.
And containing a Mn oxide as a second subcomponent,
The content b (parts by weight) of the Mn oxide is converted to MnO.
0.5 <b ≦ 20, dielectric ceramics
Mick composition. 2. The method according to claim 1, wherein the glass as the first subcomponent is B
_2. The dielectric ceramic composition according to claim 1, wherein the dielectric ceramic composition is a ₂ O ₃ —SiO ₂ system glass (not including a Pb oxide). 3. The method according to claim 1, wherein 100 parts by weight of the main component is
3. The dielectric according to claim 1, wherein Cu oxide is contained as a subcomponent of (c), and the content c (parts by weight) of the Cu oxide satisfies c ≦ 10 in terms of CuO. 4. Ceramic composition. 4. A multilayer ceramic component comprising: a plurality of dielectric ceramic layers; an internal electrode formed between said dielectric ceramic layers; and an external electrode electrically connected to said internal electrode. Claims 1-3
5. The multilayer ceramic component comprising the dielectric ceramic composition according to any one of the above, wherein the internal electrode is mainly composed of Cu or Ag.