JP2001294481A - Dielectric ceramic composition and multilayer ceramic capacitor using the same - Google Patents

Dielectric ceramic composition and multilayer ceramic capacitor using the same

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Publication number
JP2001294481A
JP2001294481A JP2001033447A JP2001033447A JP2001294481A JP 2001294481 A JP2001294481 A JP 2001294481A JP 2001033447 A JP2001033447 A JP 2001033447A JP 2001033447 A JP2001033447 A JP 2001033447A JP 2001294481 A JP2001294481 A JP 2001294481A
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dielectric
composition
dielectric ceramic
insulation resistance
multilayer ceramic
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JP3642282B2 (en
Inventor
Masatoshi Hiraga
Kazuhiro Komatsu
Masafumi Nakayama
雅文 中山
和博 小松
正寿 平賀
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Matsushita Electric Ind Co Ltd
松下電器産業株式会社
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Abstract

PROBLEM TO BE SOLVED: To provide a dielectric ceramic composition which exhibits stable electric characteristics by firing in a non-oxidizing atmosphere and to provide a multilayer ceramic capacitor. SOLUTION: The dielectric ceramic composition is obtained by adding, as additives, 0.1 to 0.7 wt.% Mn3O4, 0.5 to 3.0 wt.% BaSiO3, 0.01 to 0.07 wt.% V2O5 and 0.05 to 0.30 Al2O3 to a composition which is composed of main components expressed by general formula, n(BaOx-SrOy-CaOz)(ZrmTi1-m)O2(x+y+ z=1, x, y, z, m and n each represent molar ratio.), wherein x, y and z are each in the range obtained by surrounding points a, b, c, d and e, shown in Table 1, with straight lines, m>=0.95, and 0.8<=n<=104.

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 use in a multilayer ceramic capacitor for temperature compensation having an internal electrode formed of a base metal such as nickel, and a multilayer ceramic capacitor using the same.

[0002]

2. Description of the Related Art A conventional multilayer ceramic capacitor is obtained by forming a multilayer body in which a plurality of ceramic green sheets mainly composed of dielectric powder and internal electrode layers are alternately laminated in accordance with a known method for manufacturing a multilayer ceramic capacitor. After cutting into a chip shape to form a green chip, baking is performed at a predetermined temperature, and an external electrode is provided on the end surface of the sintered body so as to be electrically connected to the internal electrode exposed on the end surface of the obtained sintered body. The method of forming is generally performed.

[0003] In order to prevent oxidation of a green chip using a base metal such as nickel for the internal electrode, a method of sintering in a non-oxidizing atmosphere has become mainstream.

[0004]

However, a dielectric ceramic composition used for a multilayer ceramic capacitor for temperature compensation having a small temperature coefficient of capacitance is generally composed of M as a main component.
In many cases, rare earth oxides are added to gTiO 3 and CaTiO 3. When this material is fired in a non-oxidizing atmosphere, titanium oxide in the main component is easily reduced. There was a problem that characteristics could not be obtained.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a dielectric ceramic composition capable of obtaining stable electrical characteristics with high insulation resistance under firing conditions in a non-oxidizing atmosphere and a multilayer ceramic capacitor using the same. It is suitable for a multilayer ceramic capacitor for temperature compensation using a base metal such as nickel for the internal electrodes.

[0006]

In order to achieve the above object, the present invention provides a compound represented by the general formula: n (BaO x -SrO y -CaO
z) (Zr m Ti 1- m) O 2 ( where, x + y + z = 1 , x,
In the composition system represented by (y, z, m, n is a molar ratio), x, y, z are a, b, c, d, e shown in (Table 2).
Are enclosed by a straight line, m ≧ 0.95, 0.8 ≦ n ≦ 1.
04 as a main component, and the main component 1
Mn 3 O 4 as an additive is 0.1 to
0.7wt%, BaSiO 3 a 0.5~3.0wt%,
V 2 O 5 the 0.01~0.07wt%, in which further a dielectric ceramic composition obtained by adding 0.05~0.30Wt% of Al 2 O 3.

[0007]

[Table 2]

As a result, it is possible to obtain a dielectric ceramic composition having high insulation resistance and stable dielectric properties even when fired in a non-oxidizing atmosphere, and a multilayer ceramic capacitor using the same.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The invention described in claim 1 of the present invention has a general formula of n (BaO x -SrO y -CaO z )
(Zr m Ti 1-m) O 2 ( where, x + y + z = 1 , x,
In the composition system represented by (y, z, m, n is a molar ratio), x, y, z are a, b, c, d, e shown in (Table 2).
Are enclosed by a straight line, m ≧ 0.95, 0.8 ≦ n ≦ 1.
04 as a main component, and the main component 1
Mn 3 O 4 as an additive is 0.1 to
0.7wt%, BaSiO 3 a 0.5~3.0wt%,
This is a dielectric ceramic composition to which V 2 O 5 is added in an amount of 0.01 to 0.07 wt% and further Al 2 O 3 is added in an amount of 0.05 to 0.30 wt%. , C, d, and e by a combination of three molar ratios of BaO, SrO, and CaO within a range surrounded by a straight line, thereby improving the sinterability, increasing the insulation resistance, and decreasing the capacitance temperature coefficient. Also, a multilayer ceramic capacitor having a high dielectric constant and excellent dielectric properties can be obtained.

Further, by defining the molar ratio of ZrO 2 and TiO 2 within the range of m, a dielectric ceramic composition having a small capacitance temperature coefficient can be obtained. In this way, the range in which sintering can be performed in a non-oxidizing atmosphere is defined, and BaSiO 3 , A
Addition of l 2 O 3 and Mn 3 O 4 has the effect of sintering at a firing temperature of 1300 ° C. or less. Therefore, by firing at 1350 ° C. or less (preferably 1300 ° C. or less), a multilayer ceramic capacitor in which the internal electrodes are formed of nickel prevents defects such as internal electrode diffusion and a decrease in capacitance, which are likely to occur at high temperature firing. It has the effect of being able to.

The addition of a prescribed amount of Mn 3 O 4 has the effect of improving the resistance to reduction, and has the effect of preventing the insulation resistance from deteriorating even when firing in a non-oxidizing atmosphere. , V 2 O 5 has the effect of further improving the reduction resistance.

According to a second aspect of the present invention, there is provided the dielectric ceramic composition according to the first aspect, wherein 0.2 to 1.0 wt% of Y 2 O 3 is further added as an additive. This has the effect of preventing the deterioration of the insulation resistance inside the capacitor body and improving the high-temperature load life characteristics when voltage is applied.

According to a third aspect of the present invention, there is provided the dielectric material according to the first aspect, wherein 0.02 to 0.5 wt% of NiO or 0.1 to 0.5 wt% of MgO is further added as an additive. Multilayer ceramic capacitor that is a body porcelain composition that can reduce the difference in sintering shrinkage behavior of the laminate of nickel internal electrodes and ceramic sheets, prevent cracks and residual stress, and have excellent moisture load life characteristics Is obtained.

The invention described in claim 4 of the present invention is the invention
BaSiO according to any one of 1 to 3ThreeChange to
And BaO, SrO, CaO, MgO, ZnO, NaTwo
O, Li TwoO, KTwoO, BTwoOThreeAt least one selected from
More than kinds of elements and SiOTwo, AlTwoOThreeGala consisting of
The method according to claim 1, wherein 0.5 to 3.0 wt% of the frit is added.
The dielectric ceramic composition according to the above, further improving the sinterability
At 1250 ° C or lower and in a non-oxidizing atmosphere
It is possible to fire on the strong reduction side in
In many cases, multilayer ceramic cores with internal electrodes made of nickel
Heat generated during solder dip mounting on capacitors
This has the effect of preventing a target crack.

According to a fifth aspect of the present invention, a ceramic layer comprising the dielectric ceramic composition according to any one of the first to third aspects and an internal electrode of a base metal such as nickel are alternately laminated. A multilayer ceramic capacitor having a ceramic layer formed of the dielectric ceramic composition according to any one of claims 1 to 3, having a high insulation resistance even when fired in a non-oxidizing atmosphere. Because of this, the multilayer ceramic capacitor element using a base metal such as nickel for the internal electrode is fired in a non-oxidizing atmosphere to obtain a low capacitance temperature coefficient and high temperature load life characteristics and humidity load life characteristics. Thus, it is possible to obtain a multilayer ceramic capacitor for temperature compensation having excellent reliability.

According to a sixth aspect of the present invention, there is provided a multilayer ceramic capacitor in which a ceramic layer comprising the dielectric ceramic composition according to the fourth aspect and internal electrodes of a base metal such as nickel are alternately laminated. It is suitable for multi-layer ceramic capacitors with a ceramic green sheet thickness of 10 μm or less and a lamination number of 50 layers or more, and thermal cracks are less likely to occur. It has the effect that it can be obtained.

(Embodiment 1) Hereinafter, the first embodiment of the present invention will be described with reference to the first embodiment.

FIG. 1 shows a dielectric ceramic composition of the present invention.
It is an original composition diagram and shows a composition range surrounded by a straight line connecting a, b, c, d, and e shown in (Table 2).

First, as a starting material, high-purity BaO, S
rO, CaO, ZrO 2, TiO 2, Mn 3 O 4, Al
The powders of 2 O 3 , BaSiO 3 , and V 2 O 5 were weighed so as to have the composition ratios shown in (Table 3), wet-mixed, and dehydrated and dried. And calcined in air at a temperature of 1170 ° C. for 2 hours.

[0020]

[Table 3]

Next, the calcined material was put into a rubber-lined ball mill together with pure water and zirconia balls, wet-pulverized, dehydrated and dried to prepare a dielectric material for temperature compensation. An organic binder was added to the obtained dielectric material for temperature compensation, and after granulation, a molding pressure of 1 ton was applied using a hydraulic press.
A disk having a diameter of 15 mm and a thickness of 0.4 mm was formed at a thickness of 0.4 mm / cm 2 .

Next, the formed disk is placed in an alumina sheath, degreased in air at 700 ° C. for 2 hours, and then baked in a non-oxidizing atmosphere at 1300 ° C. for 2 hours to obtain a sintered disk. I got

After applying a copper electrode paste on both surfaces of the obtained sintered body, baking at a temperature of 900 ° C. in a non-oxidizing atmosphere, the dielectric constant, the capacitance temperature coefficient, and the insulation resistance were measured. The results are shown in (Table 4). The measurement of the dielectric constant was performed at a temperature of 20 ° C., a measurement voltage of 1.0 Vrms, and a measurement frequency of 1 MHz. The insulation resistance was obtained from the resistance value after applying DC 50 V between the electrodes for 1 minute.
The capacitances at ° C and 125 ° C were measured and found from (Equation 1).

[0024]

(Equation 1)

Further, a vehicle comprising butyl acetate, polyvinyl butyral, and a plasticizer was added to each powder of the dielectric composition prepared in the present invention, and a ceramic green sheet having a thickness of 28 μm was prepared by a known doctor blade method.

Using the obtained ceramic green sheets of the respective compositions, 600 kg of a green laminate in which 20 internal electrodes made of nickel metal and 20 ceramic green sheets are alternately laminated by a known method of manufacturing a laminated ceramic capacitor. After pressure-compression bonding at a pressure of / cm 2, the resultant was cut into a predetermined chip shape to obtain a green chip.

Further, after the green chip is degreased at a temperature of 400 ° C. for 2 hours or less under the equilibrium oxygen partial pressure of nickel,
In a non-oxidizing atmosphere, sintering is performed at a firing temperature of 1300 ° C. for 2 hours to form a sintered body, and a copper paste to be an external electrode is applied to an end surface of the sintered body where an internal electrode is exposed, and the non-oxidizing atmosphere is formed. Baking was performed inside, and thereafter, electrolytic plating was performed to complete a multilayer ceramic capacitor.

At this time, the surface of the element is somewhat reduced in the baking step in the non-oxidizing atmosphere, and the insulation resistance is liable to deteriorate due to adsorption of a plating solution or moisture remaining on the surface of the multilayer ceramic capacitor in the electrolytic plating step. Although having a problem, the dielectric ceramic composition of the present invention can improve the reduction resistance, so that the deterioration of the insulation resistance can be prevented.

The capacitance, Q, temperature coefficient of capacitance, and insulation resistance of each of the obtained multilayer ceramic capacitors were measured, and the results are shown in Table 4. The value of the dielectric constant is preferably 35 or more, and the capacitance temperature coefficient is 0 ±
60 ppm / ° C is preferred.

[0030]

[Table 4]

As can be seen from the results in Table 4, among the samples outside the scope of the present invention, Samples 1 to 10 have a small dielectric constant of 32 or less, and Samples 11 and 26 have a temperature coefficient of capacitance of 0 ±
60 ppm / ° C. 27,3
Sample Nos. 4 and 47 were not sintered. 33, 38, 39, 4
2, 43, 48 and 51 are not practical because the insulation resistance is 10 10 Ω or less.

On the other hand, the sample Nos.
12-25, 28-32, 35-37, 40, 41, 4
4~46,49,50 the high dielectric constant is 35 or more, and in a range temperature coefficient of capacitance of all NP0 ± 60 ppm / ° C., to obtain very good result is all also insulation resistance 10 10 Omega more Have been.

That is, the sample No. 1 to 9 are BaO, Sr
It consists of a composition system composed of one or two selected from O and CaO, is outside the range of the molar ratio shown in (Table 2) of the present invention, and has an insulation resistance of 10 10 Ω or less or a dielectric constant of 35 or less. Or, the temperature coefficient of capacitance becomes large, which is not preferable.

On the other hand, the sample N within the scope of the present invention
o. The dielectric ceramic compositions of 12 to 23 have a dielectric constant of 35 to
43, the temperature coefficient of capacitance was small, the insulation resistance was all 10 10 Ω or more, and good results were obtained. The range of the molar ratios x, y, and z was shown in FIG. 1 (Table 2). A,
The range of the molar ratio surrounding b, c, d, and e with a straight line is effective.

Further, the sample No. 26 has a molar ratio m of 0.9
0, which is outside the range of the molar ratio m of the present invention, and is preferable because the temperature coefficient of capacitance is as large as N250 as compared with the samples 24 and 25 within the range of the present invention and does not satisfy the range of 0 ± 60 ppm / ° C. Absent. Therefore, the value of the molar ratio m is defined as m ≧
It is effective to set it to 0.95.

Sample No. 27 has a molar ratio n of 1.0
5, the sample 33 has a molar ratio n of 0.60, which is outside the range of the molar ratio n of the present invention. As compared with 28 to 32, the sample 27 did not sinter,
Sample No. No. 33 is not preferable because the insulation resistance is as low as 10 9 . Therefore, the molar ratio n is effective in the range of 0.80 ≦ n ≦ 1.04.

When the amount of BaSiO 3 added was zero, the sample No. As shown in sample 38, which does not sinter as in 34, and the amount of addition exceeds 3 , SiO 2 in BaSiO 3 is easily reduced, and the insulation resistance is not more than 10 10 Ω.
On the other hand, the sample Nos. In Nos. 35 to 37, the insulation resistance was 10 10 Ω or more, and good results were obtained. Therefore, the addition range of BaSiO 3 0.5-3.
0 wt% is effective.

When the addition amount of Mn 3 O 4 is zero,
Sample No. As in No. 39, there is no reduction resistance, and the amount of addition is 0.3.
If it exceeds 7, the effect of reduction resistance is reduced as in Sample 42, and the insulation resistance is undesirably reduced to 10 10 Ω or less. On the other hand, the sample Nos. 40 and 41 have an insulation resistance of 10 10 Ω or more, and good results are obtained. Therefore, the effective range of addition of Mn 3 O 4 is 0.1 to 0.7 wt%.

When the addition amount of V 2 O 5 was zero, the sample No. No reduction resistance and insulation resistance of 10 10 like 43
When the added amount exceeds 0.07 as in the case of sample 47, sintering is stopped, which is not preferable. In contrast,
Sample No. within the scope of the present invention. 44 to 46 have an insulation resistance of 1
0 10 Ω or more, and good results were obtained. Therefore, the effective range of V 2 O 5 is 0.01 to 0.07 wt%. Particularly, the added amount of V 2 O 5 is set to 0.04 to 0.07.
If it is set to wt%, the insulation resistance is more preferably 10 12 Ω or more, and it is more preferable.

When the addition amount of Al 2 O 3 is zero, the sample N
o. As shown in Sample No. 48, the sinterability was poor. As shown by 51, the sinterability deteriorates and the insulation resistance becomes 10 10 Ω or less, which is not preferable. On the other hand, the sample Nos. 49 and 50 have insulation resistance of 10 10
Ω or more, and good results have been obtained. Therefore, Al
The effective range of addition of 2 O 3 is 0.05-0.3 wt%.

(Embodiment 2) Hereinafter, a second embodiment of the present invention will be described with reference to Embodiment 2.

After weighing the powder used in the first embodiment and Y 2 O 3 as the starting materials so as to have the composition ratio shown in (Table 5), the subsequent steps were processed under the same conditions as in the first embodiment. Thus, a dielectric porcelain disk was produced. Next, the prepared disk samples were evaluated in the same manner as in Embodiment 1, and the results are shown in (Table 6).

[0043]

[Table 5]

[0044]

[Table 6]

Embodiment 1 for each dielectric powder
Under the same conditions as above, a ceramic green sheet having a thickness of 11 μm was formed, and the obtained ceramic green sheet was used.
In the same manner as in the first embodiment, a multilayer ceramic capacitor in which nickel internal electrodes and ceramic green sheets were alternately stacked in 45 layers was completed.

The capacitance, Q, capacitance temperature coefficient, and insulation resistance of each of the obtained multilayer ceramic capacitors were measured by the same method, and the results are shown in Table 6. In addition, as an accelerated life test under a high temperature load, 3
A DC voltage of 00 V was continuously applied between the external electrodes of the multilayer ceramic capacitor for 500 hours, and the results are also shown in Table 6.

As can be seen from the results in Table 6, the present invention
Sample 52 outside the rangeTwoOThreeBecause the amount of
The effect on accelerated life test under high temperature load
Sample No. 56 does not sinter due to the large amount of addition
No. On the other hand, samples 53 to 55 within the scope of the present invention are:
Accelerated life test under high temperature load even for products with thin layers and high lamination
Good results are obtained without insulation resistance deterioration due to
You can see that. Therefore, Y TwoOThreeRange of 0.2
1.01.0 wt%. Y within the scope of the present invention
TwoOThreeFor firing in a non-oxidizing atmosphere
Oxygen vacancies that are more likely to be generated are suppressed,
Deterioration of the edge can be prevented. In addition, the deterioration of the insulation property
Insulation resistance of 109If the resistance drops below Ω,
Counted.

(Embodiment 3) Hereinafter, a third embodiment of the present invention will be described with reference to Embodiment 3.

After weighing the powders used in Embodiment 1 and NiO and MgO as the starting materials so as to have the composition ratios shown in Table 7, the subsequent steps were processed under the same conditions as in Embodiment 1. Then, a dielectric porcelain disk was produced. Next, the fabricated disk samples were evaluated in the same manner as in Embodiment 1, and the results are shown in (Table 8).

[0050]

[Table 7]

[0051]

[Table 8]

Embodiment 1 for each dielectric powder
Under the same conditions as above, a ceramic green sheet having a thickness of 11 μm was formed, and the obtained ceramic green sheet was used.
In the same manner as in the first embodiment, a multilayer ceramic capacitor in which nickel internal electrodes and ceramic green sheets were alternately stacked in 45 layers was completed.

The capacitance, Q, capacitance temperature coefficient, and insulation resistance of each of the obtained multilayer ceramic capacitors were measured, and the results are shown in Table 8. After sintering, n = 1
After performing an internal crack inspection of 00 and further performing a saturated pressure cooker test (PCT) in which pressure is applied at 2 atm for 24 hours in a constant temperature and humidity chamber of 121 ° C. and 100% RH as an accelerated life test under a moisture resistance load. 85 ° C 85
A combined humidity resistance acceleration test was conducted in which a DC voltage of 50 V was continuously applied between the external electrodes of the multilayer ceramic capacitor for 125 hours in a constant temperature and humidity chamber of% RH, and the results are also shown in Table 8.

As can be seen from the results in Table 8, the sample Nos. In Nos. 57 and 62, since the addition amounts of NiO and MgO were small, the difference in sintering shrinkage behavior between nickel and ceramic of the internal electrode was large, and cracks occurred inside the sintered body after firing. Thereafter, the number of cracks increased and insulation deterioration occurred. The deterioration of the insulation was counted as a failure when the insulation resistance after the test was reduced to 5 × 10 8 Ω or less.

The sample No. No. 61 is not appropriate because the addition amount of NiO increases, so that the reduction resistance of the element body deteriorates, and the insulation resistance after forming a multilayer ceramic capacitor deteriorates to 10 10 Ω or less. For sample 66, MgO
Is excessive, the reaction proceeds between MgO and nickel of the internal electrode, and a compound of MgNiO 2 is likely to be formed. As a result, the nickel of the internal electrode disappears, causing a variation in capacitance.

On the other hand, the sample Nos.
58 to 60 and 63 to 65, the difference in sintering shrinkage behavior between nickel of the internal electrode and the ceramic is mitigated by the additive NiO or MgO, there is no crack after sintering, and there is no variation in capacitance, The insulation resistance was 10 10 Ω or more, and it can be seen that the insulation resistance did not deteriorate even after the composite moisture resistance acceleration test, and extremely good results were obtained. Therefore, the effective range of the amount of NiO added is 0.02 to 0.5 wt%, and the effective range of the MgO is 0.2 to 0.5 wt%.

(Embodiment 4) Hereinafter, a fourth embodiment of the present invention will be described with reference to Embodiment 4.

The powders used in Embodiment 1 as starting materials and the various glass frits shown in Table 9 were used (Table 1).
After weighing so as to have the composition ratio shown in 0), the subsequent steps were processed under the same conditions as in Embodiment 1 to produce a dielectric ceramic disk. However, the firing temperature was 1250 ° C., and firing was performed in a strongly reduced non-oxidizing atmosphere. Next, the prepared disk samples were evaluated in the same manner as in Embodiment 1, and the results were obtained (Table 11).
It was shown to.

[0059]

[Table 9]

[0060]

[Table 10]

[0061]

[Table 11]

Embodiment 1 for each dielectric powder
A ceramic green sheet having a thickness of 7 μm was formed under the same conditions as described above, and the obtained ceramic green sheet was used, and in the same manner as in the first embodiment, nickel internal electrodes and ceramic green sheets were alternately laminated in 100 layers. The capacitor was completed.

The capacitance, Q, temperature coefficient of capacitance, and insulation resistance of each of the obtained multilayer ceramic capacitors were measured, and the results are shown in Table 11. In addition, as a mounting test, a thermal crack inspection using a solder dip of n = 100 was performed, and the results are also shown in Table 11. The solder temperature during the solder dip was 330 ° C., and the immersion time was 5 seconds.

As can be seen from the results shown in Table 11, the sample Nos. No. 67 has insufficient sintering due to the small amount of glass frit added, and has thermal cracks due to insufficient strength due to a large number of holes inside the dielectric ceramic, and has low insulation resistance. Sample No. In No. 79, the addition amount of the glass frit is too large, so that the reduction resistance of the dielectric porcelain is impaired, a thermal crack is generated due to the deterioration of the dielectric porcelain strength, and the insulation resistance is low.

On the other hand, the sample Nos.
Nos. 68 to 78 show that low-temperature sintering in a strong reducing atmosphere hardly generates residual stress in the element body, can prevent the occurrence of thermal cracks, and can provide a multilayer ceramic capacitor having high insulation resistance and large capacitance. It is possible.

As described above, the dielectric ceramic composition of the present invention has a dielectric constant of 35 or more, a capacitance temperature coefficient of NP0 ± 60 ppm / ° C., and a capacitance temperature change rate of NP0 ± 60 ppm / ° C. even when fired in a non-oxidizing atmosphere. Small and excellent electrical properties of dielectric porcelain can be obtained.

In particular, when a multilayer ceramic capacitor using a base metal such as nickel for the internal electrode is manufactured using the dielectric ceramic composition powder of the present invention, the insulation resistance is not degraded due to the reduction of the element surface, and the insulation resistance is 10%. 10 Ω or more, and even when ceramic layers are thin and highly laminated,
High temperature accelerated life test at 0 ° C. 300 V Continuous voltage application for 500 hours, and accelerated life test under a moisture resistant load at 121 ° C.
After performing a saturated pressure cooker test (PCT) in which pressure is applied at 2 atm for 24 hours in a constant temperature and humidity chamber of 100% RH, the temperature is adjusted to 12 at 50 V in a constant temperature and humidity chamber of 85 ° C. and 85% RH.
It is possible to obtain an extremely reliable multilayer ceramic capacitor which has no deterioration in insulation resistance even when a composite moisture resistance acceleration test in which a voltage is continuously applied for 5 hours is performed and does not generate thermal cracks even in mounting performance by solder dip. .

In Embodiments 1 to 4 of the present invention,
Therefore, BaO, SrO, CaO, Z
rOTwo, TiOTwo, AlTwoOThree, BaSiOThree, MnThreeOFour,
VTwoOFive, MgO, YTwoOThree, NiO powder and BaO,
SrO, CaO, MgO, ZnO, NaTwoO, LiTwoO,
KTwoO, BTwoOThreeAt least one element selected from
Element and SiOTwo, AlTwoOThreeComposed of glass frit
Although powder was used, Ba-Sr-Ca-Ti-Zr-O
Or Ba, Sr, Ca, Ti, Zr charcoal
Acid salts, hydroxides, etc., to form the composition of the present invention.
Also AlTwoOThree, BaSiOThreeAnd various glass free
Part, MnThreeOFour, VTwoOFive, MgO, YTwoO Three, NiO
Is added as an additive after the main component is calcined in advance.
Even if added, similar characteristics can be obtained.

[0069]

As described above, according to the present invention, it is possible to obtain a dielectric ceramic composition having a high insulation resistance and stable electric characteristics, and a multilayer ceramic capacitor using the same. In particular, the present invention is effective for a multilayer ceramic capacitor for temperature compensation in which firing is performed in a non-oxidizing atmosphere using a base metal such as nickel for the internal electrodes.

[Brief description of the drawings]

FIG. 1 is a ternary composition diagram showing the composition range of a dielectric ceramic composition of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H01B 3/12 338 H01G 4/12 358 H01G 4/12 358 361 361 C04B 35/00 E

Claims (6)

    [Claims]
  1. [Claim 1] n (BaO x -SrO y -C
    aO z) (Zr m Ti 1- m) O 2 ( where, x + y + z = 1 ,
    x, y, z, m, and n represent molar ratios), and x, y, and z are a, b, and
    m ≧ 0.95, 0.8 within a range surrounding c, d, and e by a straight line
    ≦ n ≦ 1.04 as a main component, and 0.1 to 0.7 wt% of Mn 3 O 4 and 0.5 to 3 of BaSiO 3 as additives with respect to 100 wt% of the main component. .0
    wt%, V 2 O 5 the 0.01~0.07wt%, further A
    The dielectric ceramic composition obtained by adding 0.05~0.30Wt% of l 2 O 3. [Table 1]
  2. The method according to claim 1, further Y 2 O 3 as an additive 0.2.
    The dielectric ceramic composition according to claim 1, wherein 0 wt% is added.
  3. 3. NiO is added as an additive in an amount of 0.02-
    0.5wt% or 0.1-0.5wt% MgO
    The dielectric ceramic composition according to claim 1, which is added.
  4. 4. The method according to claim 1, wherein
    BaSiOThreeInstead of BaO, SrO, CaO, Mg
    O, ZnO, NaTwoO, LiTwoO, KTwoO, BTwoO ThreeChoose from
    At least one kind of element and SiOTwo, AlTwoO
    Three0.5 to 3.0 wt% of glass frit composed of
    The dielectric ceramic composition according to claim 1, which is added.
  5. 5. A multilayer ceramic capacitor in which ceramic layers made of the dielectric ceramic composition according to claim 1 and internal electrodes of a base metal such as nickel are alternately stacked.
  6. 6. A multilayer ceramic capacitor in which ceramic layers made of the dielectric ceramic composition according to claim 4 and internal electrodes of a base metal such as nickel are alternately laminated.
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