JP2000311828A - Manufacture of dielectric ceramic composition and manufacture of dielectric layer containing electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize a method of manufacturing a layered ceramic capacitor, which can satisfy the capacitance temp. characteristics X7R (EIA standard) and B (EIAJ standard), small deterioration in capacitance over aging under d-c electric filed, a long accelerated life of insulation resistance, and small capacitance reduction under a d-c bias, even with, e.g. an ultra-thin dielectric layer which has a thickness of 4 μm or less. SOLUTION: This method of manufacturing a dielectric ceramic composition at least a main component BaTiO3, a second sub-component (Ba,Ca)xSiO2-x (where x=0.8-1.2) and other sub-components comprises the steps of mixing the main component with at least a part of the other sub-components, except for the second sub-component to prepare a powder before calcining, calcining the powder to prepare a calcined powder, and mixing at least the second sub- component to the calcined powder to obtain a dielectric ceramic compsn. having prescribed mol ratios of the sub-components to the main component BaTiO3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a dielectric ceramic composition and a method for producing a dielectric layer-containing electronic component such as a multilayer ceramic capacitor.

[0002]

2. Description of the Related Art Multilayer ceramic capacitors are small,
It is widely used as a large-capacity, high-reliability electronic component, and its number used in electrical devices and electronic devices is large. In recent years, with the miniaturization and high performance of devices, demands for further miniaturization, large capacity, low cost, and high reliability of multilayer ceramic capacitors have become more and more severe.

[0003] A multilayer ceramic capacitor is usually manufactured by laminating a paste of an internal electrode and a slurry (paste) of a dielectric by a sheet method, a printing method or the like, and firing. In general, Pd and Pd alloy have been used for such internal electrodes. However, since Pd is expensive, relatively inexpensive Ni or Ni alloy is being used. By the way, when the internal electrode is formed of Ni or a Ni alloy, there is a problem that the electrode is oxidized when firing in the air. Therefore, in general, after the binder is removed, firing is performed at an oxygen partial pressure lower than the equilibrium oxygen partial pressure of Ni and NiO, and then the dielectric layer is reoxidized by heat treatment (Japanese Patent Laid-Open No. 03-1331).
No. 16, Japanese Patent No. 2787746).

However, when firing in a reducing atmosphere, the dielectric layer is reduced and the specific resistance is reduced. Therefore, reduction-resistant dielectric materials that are not reduced even when fired in a reducing atmosphere have been proposed (I. Bur).
n, et al. , "High Resistiv
ity BaTiO ₃ Ceramics Sint
ered in CO-CO ₂ Atmosphere
es "J. Mater. Sci., 10, 6
33 (1975); Sakabe, et a
l. , "High-Dielectric Cons
tan Ceramics for Base Me
tal Monolithic Capacitor
s "pn. J. Appl. Phys., 20
Suppl. 20-4, 147 (198
1)).

However, multilayer ceramic capacitors using these reduction-resistant dielectric materials have problems that the high-temperature accelerated life of the insulation resistance (IR) is short and the reliability is low. In addition, there is a problem that the relative permittivity of the dielectric material decreases with time, which is particularly remarkable under a DC electric field. When the thickness of the dielectric layer is reduced in order to reduce the size and the capacity of the multilayer ceramic capacitor, the electric field intensity applied to the dielectric layer when a DC voltage is applied increases. For this reason, the change with time of the relative dielectric constant becomes extremely large.

[0006] By the way, X7R specified in the EIA standard
In a standard called a characteristic, the rate of change of capacity is defined to be within ± 15% between -55 ° C and 125 ° C (reference temperature 25 ° C). As a dielectric material satisfying the X7R characteristic, for example, a dielectric material described in JP-A-61-36170 is known.
A composition of aTiO ₃ + SrTiO ₃ + MnO system is known. However, this composition has a large change with time in capacitance under a DC electric field. For example, when a DC electric field of 50 V is applied at 40 ° C. for 1000 hours, the rate of change of the capacitance is −.
It becomes about 10-30%, and the X7R characteristic cannot be satisfied.

Further, a B characteristic (EI), which is a temperature characteristic of the capacitance,
In a standard called AJ standard, it is specified that the temperature is within ± 10% between −25 and 85 ° C. (reference temperature is 20 ° C.).

Further, in addition to the above, a reduction-resistant dielectric porcelain composition
An example of such a product is disclosed in Japanese Patent Application Laid-Open No. 57-71866.
BaTiO₃+ MnO + MgO, JP-A-61-
No. 250905 (Ba)_1-xS
r_xO)_aTi_1-yZr_yO₂+ Α ((1-
z) MnO + zCoO) + β ((1-t) A₂O ₅
+ TL₂O₃) + WSiO₂(However, A = N
b, Ta, V; L = Y or a rare earth element);
Ba disclosed in JP-A-83256._aCa
_1-aSiO₃Barium titanate etc.
I can do it.

However, in any of these dielectric ceramic compositions, when the thickness of the dielectric layer is, for example, an ultra-thin layer of 4 μm or less, the temperature characteristic of the capacitance, the change with time of the capacitance under a DC electric field, the insulation, It is very difficult to satisfy all of the characteristics such as the accelerated life of the resistance and the capacity reduction under DC bias. For example, those disclosed in JP-A-61-250905 and JP-A-2-832, respectively, have a problem that the accelerated life of the insulation resistance is short or the capacity is greatly reduced under DC bias.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and an object of the present invention is to provide a capacitor having a temperature characteristic of X7R even when the thickness of the dielectric layer is very thin. Characteristics (EIA standard) and B characteristic (EIAJ standard) can be satisfied, and the change with time of the capacity under a DC electric field is small, the accelerated life of insulation resistance is long, and the capacity under a DC bias is also high. An object of the present invention is to provide a manufacturing method for obtaining a dielectric layer-containing electronic component such as a multilayer ceramic capacitor with a small decrease. Further, the present invention provides a method for producing a dielectric ceramic composition suitably used as a dielectric layer of a dielectric layer-containing electronic component such as a multilayer ceramic capacitor having such excellent characteristics. With the goal.

[0011]

To achieve SUMMARY OF to the above objects, a manufacturing method of a dielectric ceramic composition according to the present invention are represented by a composition formula Ba m _TiO 2 + _n, m in the composition formula
Is 0.995 ≦ m ≦ 1.010, and n is 0.995
≦ n ≦ 1.010 and the ratio of Ba to Ti is 0.99
A main component satisfying 5 ≦ Ba / Ti ≦ 1.010, a second subcomponent serving as a sintering aid containing silicon oxide as a main component,
A method for producing a dielectric ceramic composition having at least other subcomponents, wherein the main component and at least a part of the other subcomponents are mixed except for the second subcomponent, A step of preparing a powder before calcining; a step of calcining the powder before calcining to prepare a calcined powder; and mixing at least the second subcomponent with the calcined powder. Obtaining a dielectric ceramic composition in which the ratio of each subcomponent to the main component is a predetermined molar ratio.

In a first aspect of the present invention, the second subcomponent is (Ba, Ca) _x SiO _{2 + x} (where x =
0.8 to 1.2), and the other auxiliary components are MgO, CaO, BaO, SrO and Cr.
_A first subcomponent containing at least one selected from ₂ O _{3, a third} subcomponent containing at least one selected from V ₂ O ₅ , MoO ₃ and WO _3, and an oxide of R (provided that R is at least one selected from Y, Dy, Tb, Gd and Ho), and at least a fourth subcomponent containing at least one of the second subcomponent and the calcined powder. The ratio of each subcomponent with respect to 100 mol of the main component is as follows: the first subcomponent: 0.1 to 3 mol, the second subcomponent: 2 to 12 mol, the third subcomponent: 0.1 to 3 mol, the fourth subcomponent : 0.1 to 10.0 moles (however, the number of moles of the fourth subcomponent is a ratio of R alone).

In a second aspect of the present invention, the second subcomponent is (Ba, Ca) _x SiO _{2 + x} (where x =
0.8 to 1.2), and the other auxiliary components are MgO, CaO, BaO, SrO and Cr.
_A first subcomponent containing at least one selected from ₂ O _{3, a third} subcomponent containing at least one selected from V ₂ O ₅ , MoO ₃ and WO _3, and an oxide of R (provided that R is a fourth subcomponent containing at least one selected from Y, Dy, Tb, Gd and Ho);
at least a fifth sub-component containing nO, wherein at least the second sub-component is mixed with the calcined powder, and the ratio of each sub-component to 100 mol of the main component is: 0.1 to 3 mol, 2nd subcomponent: 2 to 12 mol, 3rd subcomponent: 0.1 to 3 mol, 4th subcomponent: 0.1 to 10.0 mol (however, mol of the 4th subcomponent) The number is a ratio of R alone), and it is preferable to obtain a dielectric ceramic composition having a fifth subcomponent: 0.05 to 1.0 mol.

In this specification, each oxide constituting the main component and each subcomponent is represented by a stoichiometric composition.
The oxidation state of each oxide may deviate from the stoichiometric composition. However, the above ratio of each subcomponent is determined by converting the amount of metal contained in the oxide constituting each subcomponent to an oxide having the above stoichiometric composition. In addition, as the raw material powder of the dielectric ceramic composition, the above-described oxides and mixtures thereof, and composite oxides can be used.In addition, various compounds that become the above-described oxides and composite oxides by firing,
For example, they may be appropriately selected from carbonates, oxalates, nitrates, hydroxides, organometallic compounds and the like, and may be used as a mixture. Further, the ratio between Ba and Ca in the second subcomponent is arbitrary, and may contain only one of them.

In the present invention, the average particle size of the main component is not particularly limited, but is preferably 0.1 to 0.7 μm, and more preferably 0.2 to 0.7 μm.

In the present invention, the molar ratio of the components contained in the powder before calcination: (Ba + the metal element of the first subcomponent) / (T
i + the metal element of the fourth subcomponent) is less than 1 or (Ba +
It is preferable that the powder before calcining is prepared and calcined so that the ratio of (metal element of fourth subcomponent) / (Ti + metal element of first subcomponent) exceeds 1.

In the present invention, when preparing the powder before calcining, it is preferable that the powder before calcining always contains the first subcomponent.

In the present invention, when the raw material of the fourth subcomponent is contained in the powder before calcining, the calcining temperature is preferably 500 ° C. or more and less than 1200 ° C., and more preferably 600 ° C. or less. ９００900 ° C. When the raw material of the fourth subcomponent is not contained in the powder before calcining, the calcining temperature is preferably 600 to 1300 ° C, more preferably 900 to 1300 ° C, and particularly preferably 1000 to 1300 ° C. 120
0 ° C. Note that the calcination may be performed a plurality of times.

The calcined powder may be mixed with at least the second subcomponent. If necessary, the main component, the first subcomponent, the third subcomponent, the fourth subcomponent and the fifth subcomponent may be mixed. One or more of the subcomponents may be further mixed, and the composition of the dielectric ceramic composition finally obtained may be within the above range.

According to a third aspect of the present invention, there is provided a multilayer ceramic capacitor in which internal electrodes made of Ni or a Ni alloy and dielectric layers are alternately laminated, wherein the dielectric layer is made of BaTiO ₃ : 100 mol, MgO or Ca
At least one kind of O: 0.1 to 3 mol, MnO: 0.0
5 to 1.0 _mol, Y ₂ O 3: _0.1~5 moles, V
₂ O _5: 0.1 to 3 _moles, Ba _{a Ca 1-a} S
iO ₃ (a is a number from 0 to 1): In the method for manufacturing a multilayer ceramic capacitor comprising 2 to 12 moles in the molar ratio, and BaTiO _3, of MgO or CaO or a compound forming MgO or CaO by thermal treatment A multilayer ceramic capacitor is provided, characterized in that at least one kind is mixed in advance and a material calcined at 900 ° C. to 1300 ° C. is used in an amount of 70% by weight or more based on the whole dielectric material.

According to a fourth aspect of the present invention, there is provided a multilayer ceramic capacitor in which internal electrodes made of Ni or a Ni alloy and dielectric layers are alternately laminated, wherein the dielectric layer is made of BaTiO ₃ : 100 mol, MgO or Ca
At least one kind of O: 0.1 to 3 mol, MnO: 0.0
5 to 1.0 _mol, Y ₂ O 3: _0.1~5 moles, V
₂ O _5: 0.1 to 3 _moles, Ba _{a Ca 1-a} S
iO ₃ (a is a number from 0 to 1): In the method for manufacturing a multilayer ceramic capacitor comprising 2 to 12 moles in the molar ratio, and BaTiO _3, of MgO or CaO or a compound forming MgO or CaO by thermal treatment MnO or a compound that becomes MnO by heat treatment, Y ₂ O ₃ or Y ₂ by heat treatment
A compound which becomes O ₃ and at least one selected from the group consisting of V ₂ O ₅ or a compound which becomes V ₂ O ₅ by heat treatment are mixed in advance, and then 900 ° C. to 130 ° C.
The material calcined at 0 ° C. is applied to the entire dielectric material by 70%.
There is provided a multilayer ceramic capacitor characterized in that it is used in an amount of at least% by weight. In the third and fourth aspects of the present invention, the average particle diameter of BaTiO ₃ is 0.2 to 0.7.
μm is preferred. In the third and fourth aspects of the present invention, the number of moles of Y ₂ O ₃ is not the number of moles of Y alone but the number of moles of Y ₂ O ₃ .

[0022]

According to the conventional method for producing a dielectric ceramic composition, Ba is used.
_m TiO _{2 + n} and an additive are mixed at once to prepare a mixed powder of a dielectric ceramic composition or a dielectric paste. However, according to the conventional method, segregation of additives (first to fifth subcomponents) and the like occurs in the fired dielectric ceramic composition, and the composition of each crystal varies. Such segregation deteriorates the dielectric constant and insulation resistance of the dielectric.

According to the present invention, except for the second subcomponent, the main component is mixed with at least one of the first subcomponent, the third subcomponent, the fourth subcomponent and the fifth subcomponent. By calcining, it is possible to suppress the composition variation between the crystal grains, and as a result, it is possible to suppress the precipitation of the segregated phase and to control the size of the segregated phase. Therefore, according to the present invention, while satisfying both the X7R characteristic and the B characteristic, the change with time of the capacitance under a DC electric field is small, the accelerated life of insulation resistance is long, and the capacitance decrease under a DC electric field is small. A dielectric ceramic composition suitable for use in a dielectric layer-containing electronic component such as a multilayer ceramic capacitor having excellent reliability can be manufactured. This was first discovered by the present inventors.

The dielectric porcelain composition obtained by the production method according to the present invention has a Pb, Bi, Z
Since it does not contain an element such as n, it can be fired even in a reducing atmosphere. Therefore, Ni and Ni are used as internal electrodes.
It is possible to use a base metal such as an alloy, so that the cost can be reduced.

Further, the dielectric porcelain composition obtained by the production method according to the present invention can be used even when fired in a reducing atmosphere.
It satisfies the X7R characteristic and the B characteristic, has a small capacity aging characteristic due to the application of a DC electric field, has little deterioration in insulation resistance, and has excellent reliability. For this reason, the method of the present invention can be expected to be effective also as a technique for suppressing the deterioration of the rate of temperature change in the high temperature region due to the thinning of the multilayer capacitor.

Further, the dielectric porcelain composition obtained by the production method according to the present invention does not contain substances such as Pb and Bi, so that a product having little adverse effect on the environment due to disposal or disposal after use is provided. it can.

Further, in the manufacturing method according to the present invention, a dielectric ceramic composition having a uniform structure with a small amount of heterophase formed by depositing an additive can be realized, and the dielectric constant of the dielectric ceramic composition can be improved. Insulation resistance can be improved. In addition, the manufacturing method according to the present invention can provide a multilayer ceramic capacitor having high reliability because it is possible to prevent accidental structural defects.

Further, since the hetero-phase precipitation can be suppressed without changing the additive composition, a dielectric layer-containing electronic component such as a multilayer ceramic capacitor having a capacity-temperature characteristic satisfying the X7R characteristic and the B characteristic can be easily manufactured. be able to.

[0029]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments shown in the drawings. FIG. 1 is a sectional view of a multilayer ceramic capacitor according to one embodiment of the present invention.

Multilayer Ceramic Capacitor Before describing the method for producing the dielectric ceramic composition according to the present invention, the multilayer ceramic capacitor will be described first. As shown in FIG. 1, a multilayer ceramic capacitor 1 according to one embodiment of the present invention has a capacitor element body 10 having a configuration in which dielectric layers 2 and internal electrode layers 3 are alternately stacked. At both ends of the capacitor element body 10, a pair of external electrodes 4 are formed which are electrically connected to the internal electrode layers 3 alternately arranged inside the element body 10.
The shape of the capacitor element body 10 is not particularly limited, but is generally a rectangular parallelepiped. The dimensions are not particularly limited, and may be appropriately determined according to the application.
(0.6-5.6 mm, preferably 0.6-3.2 mm) ×
(0.3-5.0 mm, preferably 0.3-1.6 mm) ×
(0.3 to 1.9 mm, preferably 0.3 to 1.6 mm).

The internal electrode layers 3 are laminated so that each end face is alternately exposed on the surfaces of two opposing ends of the capacitor element body 10. The pair of external electrodes 4 are formed at both ends of the capacitor element body 10 and connected to the exposed end faces of the alternately arranged internal electrode layers 3 to form a capacitor circuit.

Dielectric Layer 2 The dielectric layer 2 contains the dielectric ceramic composition obtained by the manufacturing method of the present invention. The dielectric ceramic composition obtained by the production method of the present invention, a composition formula Ba _m TiO
_{2 + n} , wherein m in the composition formula is 0.995 ≦ m
≦ 1.010, and n is 0.995 ≦ n ≦ 1.010
And the ratio of Ba and Ti is 0.995 ≦ Ba / Ti ≦
1.010, and MgO, CaO, BaO,
A first subcomponent containing at least one selected from SrO and Cr ₂ O ₃ , and (Ba, Ca) _x SiO
_{2 + x} (where x = 0.8 to 1.2), V ₂ O ₅ , MoO _3, and WO ₃
A third subcomponent containing at least one selected from the group consisting of R
(Where R is Y, Dy, Tb, Gd and H
and a fourth subcomponent containing at least one selected from the group consisting of (a) and (b).

The ratio of each of the subcomponents to the main component is 0.1 to 3 mol, the second subcomponent: 2 to 12 mol, and the third subcomponent: 0.1 to 3 mol, fourth subcomponent: 0.1 to 10.0 mol. The above ratio of the fourth subcomponent is not the molar ratio of the R oxide, but the molar ratio of R alone. That is, for example, when an oxide of Y is used as the fourth subcomponent, the fact that the ratio of the fourth subcomponent is 1 mol means that the ratio of Y ₂ O ₃ is not 1 mol, but the ratio of Y is 1 mol. Means that

In this specification, each oxide constituting the main component and each subcomponent is represented by a stoichiometric composition. However, the oxidation state of each oxide may be different from the stoichiometric composition. Good. However, the above ratio of each subcomponent is determined by converting the amount of metal contained in the oxide constituting each subcomponent to an oxide having the above stoichiometric composition. In addition, as the raw material powder of the dielectric ceramic composition, the above-described oxides and mixtures thereof, and composite oxides can be used.In addition, various compounds that become the above-described oxides and composite oxides by firing, for example,
Carbonates, oxalates, nitrates, hydroxides, organometallic compounds and the like can be appropriately selected and used as a mixture.

The reasons for limiting the contents of the respective subcomponents are as follows. The first subcomponent (MgO, CaO, BaO,
If the contents of SrO and Cr ₂ O ₃ ) are too small, the effect of suppressing the capacity decrease under DC bias tends to be insufficient. On the other hand, if the content is too large, the dielectric constant tends to decrease significantly, and the accelerated life of insulation resistance tends to decrease. Note that the constituent ratio of each oxide in the first subcomponent is arbitrary.

The second subcomponent [(Ba, Ca)_xSiO
_{2 + x}BaO and CaO are also contained in the first subcomponent.
But a complex oxide (Ba, Ca)_xSiO
_{2 + x} Has low melting point and good reactivity with main components
Therefore, in the present invention, BaO and / or CaO are
It is also added as a composite oxide. Low content of second subcomponent
If too much, the sinterability is poor, the accelerated life of insulation resistance is short,
Capacitor temperature characteristics are less likely to meet X7R characteristics standards
There is a tendency. On the other hand, if the content is too high, the dielectric constant will be low.
And the capacity is reduced, and the accelerated life of insulation resistance is shortened.
Become.

_{X in} (Ba, Ca) _x SiO _{2 +} x is preferably 0.8 to 1.2, more preferably 0.9 to 1.1. When x is too small, i.e. when SiO ₂ is too large, _Ba m TiO of the main component
It reacts with _{2 + n} to deteriorate the dielectric characteristics. On the other hand, if x is too large, the melting point becomes high and the sinterability deteriorates, which is not preferable. In the second subcomponent, the ratio between Ba and Ca is arbitrary, and the second subcomponent may contain only one.

If the content of the third subcomponent (V ₂ O ₅ , MoO ₃ and WO ₃ ) is too small, the breakdown voltage tends to decrease, and the temperature characteristic of the capacitance tends to be less likely to satisfy the X7R characteristic standard. . On the other hand, if the content is too large, the initial insulation resistance tends to decrease. Note that the constituent ratio of each oxide in the third subcomponent is arbitrary.

If the content of the fourth subcomponent (R oxide) is too small, the accelerated life of insulation resistance tends to be short. On the other hand, if the content is too large, the sinterability tends to deteriorate. Among these, from the viewpoint of satisfying the X7R characteristics, among the fourth subcomponents, a Y oxide, a Dy oxide, and a Ho oxide are preferable. In particular, the property improvement effect is high,
In addition, Y oxide is preferable because it is inexpensive.

The dielectric ceramic composition of the present invention may contain MnO as a fifth subcomponent as required. The fifth subcomponent has an effect of promoting sintering and an effect of reducing dielectric loss (tan δ). In order to sufficiently obtain such an effect, it is preferable that the ratio of the fifth subcomponent to 100 mol of the main component is 0.05 mol or more. However, if the content of the fifth subcomponent is too large, the capacity-temperature characteristics are adversely affected. Therefore, the content is preferably 1.0 mol or less.

In the dielectric ceramic composition of the present invention,
In addition to the above oxides, Al₂O₃ May be included
No. Al₂O₃Has a large effect on the capacitance-temperature characteristics
Sinterability, insulation resistance and accelerated life of insulation resistance (IR
Life). Where Al₂O₃
If the content of is too large, sinterability deteriorates and IR decreases.
Therefore, Al₂O₃Is preferably 100
1 mole or less, more preferably dielectric ceramic
Not more than 1 mol of the whole composition.

It should be noted that at least one of Sr, Zr and Sn is composed of Ba in the main component of the perovskite structure.
Alternatively, when Ti is substituted, the Curie temperature shifts to a lower temperature side, so that the capacity-temperature characteristics at 125 ° C. or higher deteriorate. Therefore, _Ba m TiO containing these elements
It is preferable not to use _{2 + n} [for example, (Ba, Sr) TiO ₃ ] as a main component. However, there is no particular problem as long as it is contained as an impurity (about 0.1 mol% or less of the whole dielectric ceramic composition).

The average crystal grain size of the dielectric porcelain composition of the present invention is not particularly limited, and is, for example, 0.1 to 3.0 μm, preferably 0.1 to 0. 0 μm, depending on the thickness of the dielectric layer. 7 μm
May be appropriately determined from the range. The capacitance-temperature characteristics tend to be worse as the dielectric layer is thinner, and worse as the average crystal grain size is smaller. Therefore, when it is necessary to reduce the average crystal grain size, the dielectric ceramic composition of the present invention has an average crystal grain size of 0.1 to 0.5 μm.
This is particularly effective when. In addition, if the average crystal grain size is reduced, the IR life is prolonged, and the change with time in the capacity under a DC electric field is reduced, and from this point, the average crystal grain size is preferably small as described above. .

The dielectric layer 2 of the present invention is composed of grains, grain boundaries, and a grain boundary phase. Further, it may be composed of a composition having a so-called core-shell structure.

Various conditions such as the thickness and the number of dielectric layers composed of the dielectric ceramic composition of the present invention may be appropriately determined according to the purpose and application. For example, the thickness of the dielectric layer is
The thickness per layer is usually 50 μm or less, particularly 10 μm or less. The lower limit of the thickness is usually about 1 μm. The dielectric ceramic composition of the present invention is effective for improving the capacitance-temperature characteristics of a multilayer ceramic capacitor having such a thin dielectric layer. The number of stacked dielectric layers is usually
2 to 400, preferably about 10 to 400.

The multilayer ceramic capacitor using the dielectric porcelain composition of the present invention is particularly suitable for use as an electronic component for equipment used in an environment of -55 ° C. to + 125 ° C. Then, in such a temperature range, the temperature characteristic of the capacitance is the X7R characteristic of the EIA standard (−55 to 125 ° C.,
ΔC = ± 15%), and at the same time, the EIAJ standard B characteristic [capacity change within ± 10% at −25 to 85 ° C. (reference temperature 20 ° C.)].

In the case of a multilayer ceramic capacitor, the dielectric layer usually has a thickness of 0.02 V / μm or more, especially 0.2 V / μm.
m or more, moreover 0.5 V / μm or more, generally 5 V / μm
An AC electric field of about m or less and a DC electric field of 5 V / μm or less are superimposed on the AC electric field. Even when such an electric field is applied, the temperature characteristics of the capacitor are extremely stable.

Internal Electrode Layer 3 The conductive material contained in the internal electrode layer 3 is not particularly limited, but a base metal can be used because the constituent material of the dielectric layer 2 has reduction resistance. As the base metal used as the conductive material, Ni or a Ni alloy is preferable. The Ni alloy is selected from Mn, Cr, Co and Al.
An alloy of at least one kind of element and Ni is preferable.
The content is preferably at least 95% by weight. In addition,
Various trace components such as P are contained in Ni or Ni alloy in an amount of 0.1%.
It may be contained up to about 1% by weight. The thickness of the internal electrode layer may be appropriately determined according to the application and the like.
It is about 5 to 5 μm, preferably about 0.5 to 2.5 μm, and more preferably about 1 to 2 μm.

External electrode 4 The conductive material contained in the external electrode 4 is not particularly limited.
In the present invention, inexpensive Ni, Cu and their alloys can be used. The thickness of the external electrode may be appropriately determined according to the use or the like, but is usually preferably about 10 to 100 μm.

The multilayer ceramic capacitor produced using the production method of a dielectric ceramic composition according to the production method the present invention of a multilayer ceramic capacitor, producing a green chip by a normal printing method or sheet method using a paste After firing, the external electrodes are manufactured by printing or transferring and firing. Hereinafter, the manufacturing method will be specifically described.

First, a dielectric ceramic composition powder contained in the dielectric layer paste is prepared. As the powder of BaTiO _{3 in} the dielectric ceramic composition powder, usually, raw materials are mixed,
Not only powders obtained by a so-called solid phase method, which are calcined and pulverized, but also powders obtained by a so-called liquid phase method such as an oxalate method or a hydrothermal synthesis method may be used.

In the present invention, calcination is performed before obtaining the dielectric ceramic composition powder having the above-described composition. That is, the second by-component _(Ba, Ca) except for x _{SiO 2 + x,} M mainly _{(Ba m TiO 2 + n)} , the first subcomponent (e.g. MgO or CaO or thermal treatment
compound as a gO or CaO), the third subcomponent (for example, _V 2 _{O 5} or a compound which is a _V 2 _{O 5} by heat treatment), the fourth subcomponent (e.g. _Y 2 _{O 3} or a compound which is a _Y 2 _{O 3} by heat treatment ) And the fifth
A powder before calcining is prepared by mixing and drying at least one of the subcomponents (for example, MnO or a compound that becomes MnO by heat treatment).

It should be noted that MgO or CaO
The compound that becomes₃ , MgCl₂, M
gSO₄, Mg (NO₃)₂, Mg (O
H)₂, (MgCO₃)₄Mg (OH)₂, C
aCO₃, CaCl₂, CaSO₄, Ca (NO
₃)₂, Mg alkoxide, Ca alkoxide
And hydrates thereof. Also heat treatment
Compounds that can be converted to MnO include MnCO₃,
MnCl₂, MnSO₄, Mn (NO₃)₂What
And hydrates thereof. Also heat treatment
By Y₂O₃YCl
₃, Y₂(SO₄)₃, Y (NO₃)₃ , Y
(CH₃COO)₃, Y alkoxide or the like, or
These hydrates are exemplified. In addition, by heat treatment
V₂O₅The compound that becomes₅, V
₂(SO₄)₅, V (NO₃)₅And so on
Are exemplified by these hydrates.

The powder before calcination is then calcined. The calcination conditions are not particularly limited, but are preferably performed under the following conditions. Heating rate: 50 to 400 ° C / hour, especially 100 to 300
° C / hour, holding temperature: 500 ° C to 1300 ° C, preferably 500 ° C to less than 1200 ° C, temperature holding time: 0.5 hour to 6 hours, especially 1 to 3 hours, atmosphere: in air and in nitrogen.

The calcined calcined powder is roughly pulverized by an alumina roll or the like, and then at least (Ba, Ca) _x SiO _{2 + x} as a _second subcomponent is added. Add the additives of
The mixed powder having the final composition described above is obtained. Thereafter, the mixed powder is mixed by a ball mill or the like, if necessary, and dried to obtain a dielectric ceramic composition powder having the composition of the present invention.

The molar ratio of each component in the calcined calcined powder is not particularly limited, but preferably satisfies the following relational expression. That is, (Ba + the metal element of the first subcomponent) / (Ti + the metal element of the fourth subcomponent) is less than 1, or (Ba + the metal element of the fourth subcomponent) / (Ti + the metal element of the first subcomponent). Preferably, it exceeds 1. In such a range, the accelerated life of the insulation resistance is particularly improved.

It is preferable that the calcined powder always contains the first subcomponent. When the total weight of the first subcomponent in the final composition powder is 100% by weight, the calcined powder preferably contains 30% by weight, more preferably 50% by weight of the first subcomponent. It is preferred that

The calcined powder is used in an amount of preferably 70% by weight or more, more preferably 80% by weight or more, particularly preferably 90% by weight or more, with the dielectric ceramic composition powder finally obtained being 100% by weight. And mixed with the post-added components. If the proportion of the calcined powder is too small, the accelerated life of the insulation resistance is short, and the capacity tends to be significantly reduced under a DC bias.

Next, the dielectric ceramic composition powder thus obtained is formed into a paint to prepare a dielectric layer paste. The dielectric layer paste may be an organic paint obtained by kneading a dielectric ceramic composition powder and an organic vehicle,
A water-based paint may be used.

The particle size of the dielectric porcelain composition powder before being formed into a coating is usually about 0.1 to 3 μm, preferably about 0.1 to 0.7 μm, in average.

The organic vehicle is obtained by dissolving a binder (binder) in an organic solvent. The binder used for the organic vehicle is not particularly limited, and may be appropriately selected from various ordinary binders such as ethyl cellulose and polyvinyl butyral. Also, the organic solvent used is not particularly limited,
Depending on the method used, such as printing and sheeting, terpineol, butyl carbitol, methyl ethyl ketone,
What is necessary is just to select suitably from various organic solvents, such as acetone and toluene.

When the paste for the dielectric layer is an aqueous coating, an aqueous vehicle in which a water-soluble binder or dispersant is dissolved in water may be kneaded with a dielectric material. The water-soluble binder used for the aqueous vehicle is not particularly limited, and for example, polyvinyl alcohol, cellulose, a water-soluble acrylic resin, or the like may be used.

The paste for the internal electrode layer is made of a conductive material made of the above-mentioned various dielectric metals or alloys, or various oxides, organometallic compounds, resinates, etc. (conductive material etc.) which become the above-mentioned conductive material after firing. And kneaded with the prepared organic vehicle. The shape of the conductive material in the paste is not particularly limited, and examples thereof include a sphere and a scale, and a mixture of these shapes may be used. The external electrode paste may be prepared in the same manner as the internal electrode layer paste described above.

The content of the organic vehicle in each of the above-mentioned pastes is not particularly limited, and may be a usual content, for example, about 1 to 5% by weight of a binder and about 10 to 50% by weight of a solvent. In addition, each paste may contain auxiliary additives selected from various dispersants, plasticizers, dielectrics, insulators, and the like, as necessary. The total content of these auxiliary additives is preferably not more than 10% by weight.

As the plasticizer, for example, polyethylene glycol, phthalic acid ester (eg, dioctyl phthalate, dibutyl phthalate) and the like are used. Further, as the dispersant, for example, oleic acid, rosin, glycerin, octadecylamine, ethyl oleate, mensesden oil and the like are used.

In particular, when preparing a paste (slurry) for a dielectric layer, the content of the dielectric ceramic composition powder in the paste is about 50 to 80% by weight based on the entire paste, and the binder Is preferably about 2 to 5% by weight, the plasticizer is about 0.1 to 5% by weight, the dispersant is about 0.1 to 5% by weight, and the solvent is about 20 to 50% by weight.

When the printing method is used, the dielectric layer paste and the internal electrode layer paste are laminated and printed on a substrate such as PET, cut into a predetermined shape, and then separated from the substrate to form a green chip.

When the sheet method is used, a green sheet is formed by using a dielectric layer paste, an internal electrode layer paste is printed thereon, and these are laminated to form a green chip.

Before firing, the green chip is subjected to a binder removal treatment. The binder removal treatment may be performed under ordinary conditions. However, when a base metal such as Ni or a Ni alloy is used as the conductive material of the internal electrode layer, it is particularly preferable to perform the treatment under the following conditions. Heating rate: 5 to 300 ° C / hour, especially 10 to 100 ° C / hour
Time, holding temperature: 180 to 400 ° C, especially 200 to 300 ° C, Temperature holding time: 0.5 to 24 hours, especially 5 to 20 hours, Atmosphere: in air.

The atmosphere at the time of firing the green chip may be appropriately determined according to the type of the conductive material in the internal electrode layer paste. In the case where a base metal such as Ni or a Ni alloy is used as the conductive material, the firing atmosphere may be changed. Oxygen partial pressure is preferably 1
^0-7 to ^10-13 atm, more preferably 10 atm
^-10 to ^10-12 atm. If the oxygen partial pressure is less than the above range, the conductive material of the internal electrode layer may abnormally sinter and be interrupted. If the oxygen partial pressure exceeds the above range, the internal electrode layer tends to be oxidized.

The holding temperature during firing is preferably 1
100-1400 ° C, more preferably 1150-140
0 ° C, more preferably 1200 to 1300 ° C.
If the holding temperature is less than the above range, the densification becomes insufficient, and if the holding temperature exceeds the above range, the electrode is interrupted due to abnormal sintering of the internal electrode layer, the deterioration of the capacitance temperature characteristic due to the diffusion of the internal electrode layer constituent material, the dielectric Reduction of the body porcelain composition is likely to occur.

Preferably, various conditions during firing other than the above conditions are selected from the following ranges. Heating rate: 100 to 900 ° C / hour, especially 200 to 90
0 ° C./hour, temperature holding time: 0.5 to 8 hours, especially 1 to 3 hours, cooling rate: 50 to 500 ° C./hour, especially 200 to 300
° C / hour. Note that the firing atmosphere is preferably a reducing atmosphere. As the atmosphere gas, for example, a mixed gas of N ₂ and H ₂ is preferably used after being humidified.

When firing in a reducing atmosphere, the capacitor element body is preferably annealed. Annealing is a process for re-oxidizing the dielectric layer, which can significantly increase the IR life, thereby improving reliability.

The oxygen partial pressure in the annealing atmosphere is 10 ^−4.
It is preferable to set it to 10 to ⁷ atm. When the oxygen partial pressure is less than the above range, it is difficult to reoxidize the dielectric layer, and when the oxygen partial pressure exceeds the above range, the internal electrode layer tends to be oxidized.

The holding temperature at the time of annealing is preferably 1200 ° C. or less, particularly preferably 500 to 1200 ° C. If the holding temperature is lower than the above range, the oxidation of the dielectric layer becomes insufficient, so that the IR is low and the IR life tends to be short. On the other hand, when the holding temperature exceeds the above-mentioned range, not only the internal electrode layer is oxidized and the capacity is reduced, but also the internal electrode layer reacts with the dielectric substrate, so that the capacity-temperature characteristic deteriorates and I
A reduction in R and a reduction in IR life are likely to occur. Note that the annealing may include only the temperature increasing process and the temperature decreasing process. That is, the temperature holding time may be set to zero. In this case, the holding temperature is synonymous with the maximum temperature.

Various conditions during annealing other than the above conditions are as follows.
It is preferable to select from the following range. Temperature holding time: 0.5 to 12 hours, especially 6 to 10 hours, Cooling rate: 50 to 600 ° C / hour, especially 100 to 300
° C / hour It is preferable to use a humidified N ₂ gas or the like as the atmosphere gas.

In the above-described binder removal processing, firing and annealing, for example, a wetter or the like may be used to humidify the N ₂ gas or the mixed gas. in this case,
The water temperature is preferably about 5 to 75C.

The binder removal processing, firing and annealing are performed as follows.
It may be performed continuously or independently. When these are continuously performed, after removing the binder, the atmosphere is changed without cooling, and then the temperature is raised to the holding temperature at the time of firing, firing is performed, and then cooling is performed, and the temperature reaches the holding temperature of annealing. It is preferable to perform the annealing while changing the atmosphere. On the other hand, when performing these independently, at the time of firing, after raising the temperature under N ₂ gas atmosphere with N ₂ gas or wet to the holding temperature of the binder removal processing, further continuing the heating to change the atmosphere After cooling to the holding temperature at the time of annealing, it is preferable to change to an N ₂ gas or humidified N ₂ gas atmosphere again and continue cooling. In annealing, N ₂
After the temperature is raised to the holding temperature in the gas atmosphere, the atmosphere may be changed, or the entire annealing process may be performed in a humidified N ₂ gas atmosphere.

The end of the capacitor element body obtained as described above is polished by, for example, barrel polishing or sand blasting, and the external electrode paste is printed or transferred and baked to form the external electrode 4. The firing condition of the external electrode paste is preferably, for example, about 600 minutes to about 800 ° C. for about 10 minutes to about 1 hour in a humidified mixed gas of N ₂ and H ₂ . Then, if necessary, a coating layer is formed on the surface of the external electrode 4 by plating or the like.

The multilayer ceramic capacitor of the present invention manufactured as described above has a capacitance temperature change rate that satisfies the EIA standard X7R characteristic even when the thickness of the dielectric layer is as thin as 4 μm or less. Satisfies the EIAJ standard B characteristics. Further, the multilayer ceramic capacitor of the present invention has a small change with time in capacitance under a DC electric field, a long accelerated life of insulation resistance, and a small decrease in capacitance under DC bias.

The multilayer ceramic capacitor of the present invention thus manufactured is mounted on a printed circuit board or the like by soldering or the like, and is used for various electronic devices and the like.

The present invention is not limited to the above-described embodiment, and can be variously modified within the scope of the present invention. For example, the dielectric porcelain composition obtained by the manufacturing method according to the present invention is not limited to being used only for a multilayer ceramic capacitor, but may be used for other electronic components on which a dielectric layer is formed.

[0083]

EXAMPLES Hereinafter, the present invention will be described based on more detailed examples, but the present invention is not limited to these examples.

Example 1 Samples A1 to A10 of a multilayer ceramic capacitor were manufactured by the following procedure. First, the following pastes were prepared.

Dielectric Layer Paste First, a main component material and a subcomponent material were prepared. As the main component raw material, a particle size of 0.2 to
0.7 μm BaTiO ₃ was used. MgO and M
Carbonate was used as the raw material of nO, and oxide was used as the raw material of the other subcomponents. As a magnesium carbonate as a raw material of MgO, (MgCO ₃ ) ₄ Mg (OH) _2.5
H ₂ O was used. Further, MnCO ₃ was used as a carbonate as a raw material of MnO.

The raw material of the second subcomponent includes (Ba)
_0.6 Ca _0.4 ) SiO ₃ was used. In addition,
(Ba _0.6 Ca _0.4 ) SiO ₃ is made of BaCO
₃ , CaCO ₃ and SiO ₂ were wet-mixed by a ball mill for 16 hours, dried, fired at 1150 ° C. in air, and wet-ground by a ball mill for 100 hours.

First, BaTiO _{3 as} a main component and magnesium carbonate as a raw material of a first subcomponent are mixed,
By drying, powder before calcination was prepared. As shown in Table 1, the powder before calcining was 100 mol of BaTiO ₃
Contained 2.1 moles of magnesium carbonate in terms of MgO. The molar ratio of the specific component in the powder before calcination: (Ba + the metal element M in the first subcomponent)
g) / (Ti + metal element Y in fourth subcomponent) was found to be 1.021, as shown in Table 1. Also,
Molar ratio: (Ba + metal element Y in fourth subcomponent) / (Ti
+ The metal element Mg in the first subcomponent was examined.
As shown in FIG.

Next, the powder before calcining was calcined. The calcination conditions were as follows. Temperature rising rate: 300 ° C./hour, holding temperature (T1 in Table 1): 500 to 1350 ° C., temperature holding time: 3 hours, atmosphere: in air.

The material obtained by this calcining was pulverized for 1 hour with a raikai machine to form a calcined powder, and then the calcined powder was subjected to 3.0 as shown in Table 2. Molar (Ba _0.6 Ca _0.4 ) SiO ₃ , 0.375
Mole of MnCO ₃ , 0.1 mole of V ₂ O ₅ , and 2.1 mole of Y ₂ O ₃ (the number of moles of Y is 4.2 moles, the same applies hereinafter), and wet with a zirconia ball mill for 16 hours. After mixing, the mixture was dried to obtain a dielectric ceramic composition powder having a final composition.

100 parts by weight of the dielectric ceramic composition powder thus obtained, 4.8 parts by weight of acrylic resin, 40 parts by weight of methylene chloride, 20 parts by weight of ethyl acetate, and 6 parts by weight of mineral spirit And 4 parts by weight of acetone were mixed by a ball mill for 16 hours to form a paste.

Internal electrode layer paste 44.6 parts by weight of Ni particles having an average particle diameter of 0.4 μm, terbineol: 52.0 parts by weight, ethyl cellulose:
3.0 parts by weight and 0.4 parts by weight of benzotriazole were kneaded with a three-roll mill to form a paste.

100 parts by weight of Cu particles having an average particle diameter of 2 μm for the external electrode paste, 35 parts by weight of an organic vehicle (8 parts by weight of ethyl cellulose resin dissolved in 92 parts by weight of butyl carbitol) and 7 parts by weight of butyl carbitol Was kneaded to form a paste.

Production of Green Chip Using the above-mentioned dielectric layer paste, a PET film was formed on a PET film.
A green sheet having a thickness of 5 μm was formed. After printing the paste for internal electrodes on the surface of this green sheet, PE
The sheet was peeled off from the T film. Next, four layers of the green sheet after printing the internal electrode layer paste are sandwiched and laminated by a plurality of protective green sheets (ones on which the internal electrode layer paste is not printed).
The green chip was obtained by pressure bonding under the condition of 5 Pa.

Firing First, the green chip is cut into a predetermined size and subjected to binder removal processing, firing and annealing under the following conditions.
External electrodes were formed to obtain samples A1 to A10 of the multilayer ceramic capacitor having the configuration shown in FIG.

Binder removal processing conditions Temperature rising rate: 15 ° C./hour, holding temperature: 280 ° C., temperature holding time: 8 hours, atmosphere: in air.

Firing conditions : temperature rising rate: 200 ° C./hour, holding temperature: 1270 ° C., temperature holding time: 2 hours, cooling rate: 300 ° C./hour, atmosphere gas: humidified N ₂ + H ₂ mixed gas, oxygen partial pressure : ^10-12 atm.

Annealing condition holding temperature: 1000 ° C., temperature holding time: 3 hours, cooling rate: 300 ° C./hour, atmosphere gas: humidified N ₂ gas, oxygen partial pressure: 10 ⁻⁶ atm. The humidification of each atmosphere gas during the binder removal processing, firing and annealing is performed by setting the water temperature to 35 ° C.
Was used.

External Electrode The external electrode is obtained by polishing the end face of the fired body by sandblasting, transferring the paste for external electrode to the end face, and firing the paste at 800 ° C. for 10 minutes in a humidified N ₂ + H ₂ atmosphere. Formed.

The size of each sample thus obtained was 3.2 mm × 1.6 mm × 1.4 mm, the number of dielectric layers sandwiched between the internal electrode layers was 4, and its thickness was 3 μm.
m, and the thickness of the internal electrode layer was 1.3 μm.

In addition to the capacitor sample, a disk sample was also prepared. This disk-shaped sample had the same composition as the dielectric layer of the capacitor sample and the same sintering conditions, and was formed by coating an In-Ga electrode having a diameter of 5 mm on both surfaces of the sample.

The following characteristics were evaluated for each sample. The relative dielectric constant (εr) of the disc-shaped sample was measured at 25 ° C. with an LCR meter under the conditions of 1 kHz and 1 Vrms. Then, the relative dielectric constant was calculated from the capacitance, the electrode dimensions, and the thickness of the sample. Table 2 shows the results. The higher the relative permittivity, the better.

Breakdown voltage (VB) Breakdown voltage was measured for a sample of a multilayer chip capacitor.
A DC voltage is applied at a boosting speed of 100 V / sec.
It was determined by measuring the voltage when a leakage current of 0 mA was observed. Table 2 shows the results. The higher the breakdown voltage, the better.

IR life under DC electric field (high temperature accelerated life:
In the table, an acceleration test was performed on a sample of a HALT multilayer chip capacitor at 180 ° C. under an electric field of 10 V / μm, and the insulation resistance (I
The time until R) became 2 × 10 ⁵ Ω or less was defined as the lifetime. Table 2 shows the results. The longer the life, the better the durability of the capacitor.

Temperature characteristics of capacitance (TCC in the table) -55 to +1
The capacity was measured in a temperature range of 25 ° C., and it was examined whether or not the X7R characteristics were satisfied. Note that an LCR meter was used for the measurement, and the measurement voltage was 1 V. It was examined whether or not the capacity change rate was within ± 15% (reference temperature 25 ° C.). When satisfied, it was evaluated as ○, and when it was not satisfied, as ×.

Regarding the B characteristic, the capacitance was measured at a measurement voltage of 1 V at −25 to 85 ° C. with an LCR meter, and the rate of change of the capacitance was within ± 10% (reference temperature of 20 ° C.).
Was checked to see if it was satisfied. When satisfied, it was evaluated as ○, and when it was not satisfied, as ×.

[0106]Temporal change of capacity under DC electric field For the multilayer chip capacitor sample,
DC electric field of 2.5 V per 1 μm (applied to sample
Voltage of 7.5 V) at 40 ° C. for 100 hours.
After leaving at room temperature for 24 hours under no load condition,
Measured and capacitance C before DC electric field application₀(Initial capacity)
Of the change ΔC, and the change rate ΔC / C₀ Was calculated.
The capacity was measured under the above conditions.

The capacitance was measured at room temperature while applying a DC electric field of 0 to 13 V / μm using a capacitance-reducing LCR meter under a DC bias, and the electric field at which the capacitance under the DC electric field became −50% was determined. At least 6.3V /
μm or more, preferably 6.5 V / μm or more.

[0108]

[Table 1]

[0109]

[Table 2] Comparative Example 1 As shown in Tables 1 and 2, the main component was not calcined.
BaTiO₃: 100 mol, calculated as MgO
2.1 mol of (MgCO₃)₄Mg (OH) ₂・
5H₂O, 0.375 mol MnCO₃3.0 m
(Ba_0.6 Ca_0.4) SiO₃, 0.1 m
Le V₂O₅, And 2.1 moles of Y₂O₃To
Except for baking using the mixed powder added,
In the same manner as the sample of Example 1, a cylindrical sample and
A capacitor sample A11 was prepared and was the same as in Example 1.
Tests were conducted. Table 2 shows the results.

Example 2 As shown in Table 1, except that CaO was used as the first subcomponent and the calcination temperature was 1000 ° C. and 1100 ° C.
In the same manner as in Example 1, columnar samples and capacitor samples B1 and B2 were prepared, and the same tests as in Example 1 were performed. Table 2 shows the results.

Incidentally, the molar ratio of the specific component in the powder before calcination:
When (Ba + Ca) / (Ti + Y) was examined, it was 1.021 as shown in Table 1. The molar ratio: (B
When (a + Y) / (Ti + Ca) was examined, it was 0.9794 as shown in Table 1.

[0112]Example 3 As shown in Table 1, in the powder before calcining, as a fourth component,
2.1 moles of Y₂O ₃Or 2.1 moles of Y₂
O₃And 0.375 mol of MnCO₃And
Except that the calcining temperature was 700 to 1100 ° C.
In the same manner as in Example 1, a cylindrical sample and a capacitor
Samples C1 to C10 were prepared and tested in the same manner as in Example 1.
Test was carried out. Table 2 shows the results.

Incidentally, the molar ratio of the specific component in the powder before calcination:
When (Ba + Mg) / (Ti + Y) was examined, it was 0.9798 as shown in Table 1. Also, the molar ratio:
When (Ba + Y) / (Ti + Mg) was examined, it was 1.0206 as shown in Table 1.

[0114]Example 4 As shown in Table 1, in the powder before calcining, as a third component
0.1 mole V₂O₅ , As a fourth component, a fourth component
2.1 moles of Y₂O₃, 0.3 as the fifth component
75 moles of MnCO₃And further added, and calcining temperature
As in Example 1 except that the temperature was changed to 500 to 1300 ° C.
To obtain a cylindrical sample and a capacitor sample D1.
To D9 were prepared, and the same test as in Example 1 was performed. result
Are shown in Table 2.

Incidentally, the molar ratio of the specific component in the powder before calcination:
When (Ba + Mg) / (Ti + Y) was examined, it was 0.9798 as shown in Table 1. Also, the molar ratio:
When (Ba + Y) / (Ti + Mg) was examined, it was 1.0206 as shown in Table 1.

Example 5 As shown in Table 1, Dy ₂ O ₃ or Ho ₂ O ₃ was used instead of Y ₂ O ₃ as the fourth component at a content of 2.1 mol to obtain a powder before calcination. And the calcination temperature is 80
A cylindrical sample and capacitor samples E1 and E2 were prepared in the same manner as in Example 4 except that the temperature was changed to 0 ° C., and the same test as in Example 1 was performed. Table 2 shows the results.

Incidentally, the molar ratio of the specific component in the powder before calcination:
When (Ba + Mg) / (Ti + Dy or Ho) was examined, it was 0.9798 as shown in Table 1. Also, the molar ratio: (Ba + Dy or Ho) / (Ti + M
g), as shown in Table 1, 1.0206
Met.

Example 6 As shown in Table 1, in place of Y ₂ O ₃ as the fourth component, 1.5 mol of Gd ₂ O ₃ was used (the number of mols of Gd is 3.0 mol, and so on). Example 4 except that the content was contained in the powder before calcination and the calcination temperature was 800 ° C.
In the same manner as in the above, a columnar sample and a capacitor sample E3 were prepared, and the same test as in Example 4 was performed. Table 2 shows the results.

Incidentally, the molar ratio of the specific component in the powder before calcination:
When (Ba + Mg) / (Ti + Gd) was examined, Table 1 was obtained.
As shown in FIG. Also, the molar ratio:
When (Ba + Gd) / (Ti + Mg) was examined, Table 1 was obtained.
As shown in FIG.

[0120]Comparative Example 2 As shown in Tables 1 and 2, the main component was not calcined.
BaTiO₃: 100 mol, calculated as MgO
2.5 mol of (MgCO₃)₄Mg (OH) ₂・
5H₂O, 0.375 mol MnCO₃3.0 m
(Ba_0.6 Ca_0.4) SiO₃, 0.1 m
Le V₂O₅, And 1.5 mol of Gd₂O₃
Except that calcination was performed using the mixed powder to which
In the same manner as the sample of Example 6, a cylindrical sample and
And capacitor sample E4 were prepared and the same as in Example 6.
Tests were conducted. Table 2 shows the results.

Example 7 As shown in Table 1, instead of Y ₂ O ₃ as the fourth component, 0.7 mole of Tb ₄ O ₇ was used (the number of moles of Tb is 2.8 moles, and so on). Example 4 except that the content was contained in the powder before calcination and the calcination temperature was 800 ° C.
In the same manner as in the above, a cylindrical sample and a capacitor sample E5 were prepared, and the same test as in Example 4 was performed. Table 2 shows the results.

The molar ratio of the specific components in the powder before calcination:
When (Ba + Mg) / (Ti + Tb) was examined, Table 1 was obtained.
As shown in FIG. Also, the molar ratio:
When (Ba + Tb) / (Ti + Mg) was examined, Table 1 was obtained.
As shown in FIG.

[0123]Comparative Example 3 As shown in Tables 1 and 2, the main component was not calcined.
BaTiO₃: 100 mol, calculated as MgO
2.5 mol of (MgCO₃)₄Mg (OH) ₂・
5H₂O, 0.375 mol MnCO₃3.0 m
(Ba_0.6 Ca_0.4) SiO₃, 0.1 m
Le V₂O₅, And 0.7 mol of Tb₄O₇
Except that calcination was performed using the mixed powder to which
In the same manner as the sample of Example 7, a cylindrical sample and
And capacitor sample E6 were prepared and the same as in Example 7.
Tests were conducted. Table 2 shows the results.

Example 8 The powder before calcining contained 60 to 80 mol of BaTiO ₃ , and contained magnesium carbonate in the amount shown in Table 3 in terms of MgO. As shown in Table 4, a circle was prepared in the same manner as in Example 1 except that a main component and an auxiliary component which were not calcined were additionally added so that the weight% of the calcined component was 60 to 80% by weight. Columnar samples and capacitor samples F1 to F3 were prepared, and the same tests as in Example 1 were performed. Table 2 shows the results.

Incidentally, the molar ratio of the specific component in the powder before calcination:
When (Ba + Mg) / (Ti + Y) was examined, it was 1.021 as shown in Table 1. The molar ratio: (B
When (a + Y) / (Ti + Mg) was examined, it was 0.9794 as shown in Table 1.

[0126]

[Table 3]

[0127]

[Table 4] As shown in Evaluation Tables 1 to 4, in Examples of the present invention, all of X7
It was confirmed that the R characteristics and the B characteristics could be satisfied. Also, sample number A11 of Comparative Example 1 and sample numbers A1 to A10, B1, B2, and C1 to C of Example 1
By comparing D1, D1 to D9, E1, E2 and F1 to F3, the example has a longer IR accelerated life,
It was confirmed that the change of the capacitance under the DC electric field with the passage of time was small, and that the electric field at half the capacitance under the DC electric field was high.

Also, for example, by comparing sample number A11 as a comparative example with sample numbers D2 to D5 as examples, it is possible to appropriately select the composition of the powder before calcination and the calcination temperature, It was confirmed that the breakdown voltage could be improved.

Further, sample numbers C1 to C10 and D
By observing the results of Nos. 1 to D9, when the powder before calcining contains the fourth subcomponent, the calcining temperature is 500 ° C. or higher and 1 ° C.
It was confirmed that a temperature of less than 200 ° C., preferably 600 to 900 ° C. was preferable. In addition, by observing the results of sample numbers A1 to A10, if the raw material of the fourth subcomponent is not contained in the powder before calcining, the calcining temperature is preferably 600 to 1300 ° C. More preferably, 900 to 13
It was confirmed that the temperature was 00 ° C, particularly preferably 1000 to 1200 ° C.

Further, sample numbers A1 to A10 and D1
To D9, the molar ratio of the components contained in the powder before calcination: (Ba + the metal element of the first component) / (Ti +
The fourth component metal element) is less than 1 or a molar ratio: (T
It was confirmed that when i + the metal element of the fourth component / (Ba + the metal element of the first component) exceeds 1, the IR life and breakdown voltage characteristics are particularly improved.

Further, by comparing sample numbers F1 to F3, the calcined powder was replaced with the entire dielectric material by 10%.
0% by weight, 70% by weight or more, preferably 80% by weight
It was confirmed that it is preferable to use the above. Also, 7
When the content was less than 0% by weight, it was confirmed that the DC-Bias characteristics were completely reduced.

By observing the results of sample numbers E3 to E6, Tb oxide or Gd
Even when an oxide was used, it was confirmed that the calcining method according to the present invention did not satisfy the X7R characteristics, but improved other characteristics (particularly, IR life).

[Brief description of the drawings]

FIG. 1 is a sectional view of a multilayer ceramic capacitor.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Multilayer ceramic capacitor 2 ... Dielectric layer 3 ... Internal electrode layer 4 ... External electrode 10 ... Capacitor element main body

Claims (13)

[Claims] 1. A expressed by a composition formula _Ba m _{TiO 2 + n,} m in the composition formula is 0.995 ≦ m ≦ 1.010, n is 0.995 ≦ n ≦ 1.010, and Ba A dielectric having at least a main component having a ratio of Ti to 0.995 ≦ Ba / Ti ≦ 1.010, a second subcomponent as a sintering aid containing silicon oxide as a main component, and other subcomponents. A method for producing a body porcelain composition, wherein the main component and at least a part of other subcomponents are mixed except for the second subcomponent to prepare a powder before calcining. Preparing the calcined powder by calcining the powder before calcining; and mixing at least the second subcomponent with the calcined powder, Obtaining a dielectric porcelain composition having a predetermined molar ratio; and a dielectric porcelain composition comprising: Manufacturing method. 2. The method according to claim 1, wherein the second subcomponent is (Ba, Ca) _x S
iO _{2 + x} (where x = 0.8 to 1.2), wherein the other subcomponents are MgO, CaO, BaO, SrO and Cr ₂ O ₃
A first subcomponent containing at least one selected from the group consisting of V ₂ O ₅ , MoO ₃ and WO _{3; a} third subcomponent containing at least one selected from V ₂ O ₅ , MoO ₃ and WO _3, and an oxide of R (where R is Y , Dy, Tb, Gd and Ho), at least one of which is selected from the group consisting of Dy, Tb, Gd and Ho). The ratio of each subcomponent with respect to the moles is as follows: the first subcomponent: 0.1 to 3 mol; the second subcomponent: 2 to 12 mol; the third subcomponent: 0.1 to 3 mol; 2. The dielectric ceramic composition according to claim 1, wherein the dielectric ceramic composition has 1 to 10.0 mol (where the number of moles of the fourth subcomponent is a ratio of R alone). 3. Method of manufacturing a product. 3. The method according to claim 2, wherein the second subcomponent is (Ba, Ca) _x S
iO _{2 + x} (where x = 0.8 to 1.2), wherein the other subcomponents are MgO, CaO, BaO, SrO and Cr ₂ O ₃
A first subcomponent containing at least one selected from the group consisting of V ₂ O ₅ , MoO ₃ and WO _{3; a} third subcomponent containing at least one selected from V ₂ O ₅ , MoO ₃ and WO _3, and an oxide of R (where R is Y , Dy, Tb, Gd, and Ho), and at least a fifth subcomponent containing MnO. The calcined powder contains the second subcomponent. At least, the ratio of each subcomponent with respect to 100 mol of the main component is as follows: the first subcomponent: 0.1 to 3 mol, the second subcomponent: 2 to 12 mol, and the third subcomponent: 0.1 to 3 mol. The fourth subcomponent: 0.1 to 10.0 mol (the number of moles of the fourth subcomponent is a ratio of R alone), the fifth subcomponent: 0.05 to 1.0 mol. The method for producing a dielectric ceramic composition according to claim 1, wherein the dielectric ceramic composition is obtained. . 4. The molar ratio of components contained in the powder before calcination: (Ba + metal element of first subcomponent) / (Ti + metal element of fourth subcomponent) is less than 1 or (Ba + 4th metal element). The powder before calcining is prepared and calcined so that the ratio of (metal element of the sub-component) / (Ti + metal element of the first sub-component) exceeds 1. 4. A method for producing a dielectric ceramic composition. 5. The method according to claim 2, wherein when preparing the powder before calcination, the powder before calcination always contains the first subcomponent. A method for producing a dielectric ceramic composition. 6. The pre-calcined powder is heated at 500 ° C. or more to 120 ° C.
2. A calcination at a temperature lower than 0.degree. C.
6. The method for producing a dielectric ceramic composition according to any one of items 5 to 5. 7. The method for producing a dielectric ceramic composition according to claim 6, wherein the calcination is performed a plurality of times. 8. An average particle size of the main component is 0.1 to 0.7.
The method for producing a dielectric porcelain composition according to any one of claims 1 to 7, wherein the thickness is μm. 9. The dielectric ceramic composition according to claim 1, wherein the calcined powder is used in an amount of 70% by weight or more, based on 100% by weight of the whole dielectric material. Manufacturing method. 10. A method for producing a dielectric layer-containing electronic component, comprising forming a dielectric layer using the dielectric ceramic composition obtained by the method according to claim 1. 11. An internal electrode made of Ni or a Ni alloy
And ceramic layers alternately laminated
The dielectric layer is made of BaTiO. ₃: 10
0 mol, at least one of MgO and CaO: 0.1
３3 mol, MnO: 0.05-1.0 mol, Y₂O
₃: 0.1 to 5 mol, V₂O₅: 0.1-3mo
Le, Ba_aCa_1-aSiO₃(A is a number from 0 to 1
): Laminated ceramic containing 2 to 12 moles in this molar ratio
A method of manufacturing a mic capacitor, comprising:₃And MgO or CaO or heat treatment
Therefore, at least one of the compounds that become MgO or CaO
Wood pre-mixed with seeds and calcined at 900-1300 ° C
Material is used in an amount of 70% by weight or more based on the entire dielectric material
Manufacturing method of multilayer ceramic capacitor characterized by the following
Law. 12. An internal electrode made of Ni or a Ni alloy
And ceramic layers alternately laminated
The dielectric layer is made of BaTiO. ₃: 10
0 mol, at least one of MgO and CaO: 0.1
３3 mol, MnO: 0.05-1.0 mol, Y₂O
₃: 0.1 to 5 mol, V₂O₅: 0.1-3mo
Le, Ba_aCa_1-aSiO₃(A is a number from 0 to 1
): Laminated ceramic containing 2 to 12 moles in this molar ratio
A method of manufacturing a mic capacitor, comprising:₃And MgO or CaO or heat treatment
Therefore, at least one of the compounds that become MgO or CaO
Species and MnO or a compound that becomes MnO by heat treatment
Thing, Y₂O₃Or by heat treatment₂O₃To
And V₂O₅Or by heat treatment
V₂O₅Selected from the group consisting of
At least one of them is mixed in advance and temporarily set at 900 ° C to 1300 ° C.
The baked material should not exceed 70% by weight of the total dielectric material.
Multilayer ceramic capacitor characterized by being used above
Manufacturing method. 13. The average particle diameter of BaTiO ₃ is from 0.2 to 0.2.
11. The structure according to claim 11, wherein the thickness is 0.7 μm.
3. The method for manufacturing a multilayer ceramic capacitor according to item 2.