JP2003192432A - Dielectric ceramic composition and electronic parts - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dielectric ceramic composition having a high relative dielectric constant and the volume temperature characteristics satisfying the X8R characteristics by the EIA standard (at -55 to 150°C and within ±15% of ΔC), calcinable in a reducing atmosphere and having excellent mechanical strength. <P>SOLUTION: The dielectric ceramic composition comprises BaTiO<SB>3</SB>as the main component and at least a first assistant component containing at least one kind selected from MgO, CaO, BaO, SrO and Cr<SB>2</SB>O<SB>3</SB>, a second assistant component expressed by (Ba, Ca)<SB>x</SB>SiO<SB>2+x</SB>, wherein x ranges from 0.8 to 1.2, a third assistant component containing at least one kind selected from V<SB>2</SB>O<SB>5</SB>, MoO<SB>3</SB>and WO<SB>3</SB>, a fourth assistant component containing an oxide of R1, wherein R1 is Yb, and a fifth assistant component containing an oxide of R2, wherein R2 is at least one kind selected from Y, Dy, Ho, Tb, Gd and Eu. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reduction-resistant dielectric ceramic composition and an electronic component such as a laminated ceramic capacitor using the same, and more specifically, it has a capacitance-temperature characteristic of X8R of EIA standard. Characteristics (-55 to 150
The present invention relates to a dielectric porcelain composition that satisfies the requirements of ° C and ΔC = within ± 15%) and can improve the mechanical strength of electronic parts.

[0002]

2. Description of the Related Art A monolithic ceramic capacitor as an electronic component is widely used as a small-sized, large-capacity, high-reliability electronic component, and a large number is used in one electronic device. In recent years, with the miniaturization and high performance of equipment, further miniaturization of multilayer ceramic capacitors,
The demands for large capacity, low price, and high reliability are becoming more and more severe.

In a multilayer ceramic capacitor, an internal electrode layer paste and a dielectric layer paste are usually laminated by a sheet method or a printing method, and the internal electrode layer and the dielectric layer in the laminated body are simultaneously fired. Manufactured.

Generally, Pd is used as a conductive material for the internal electrode layers.
Although Pd and Pd alloys are used, since Pd is expensive, relatively inexpensive base metals such as Ni and Ni alloys have been used. When a base metal is used as the conductive material of the internal electrode layer, the internal electrode layer is oxidized when firing in the air. Therefore, it is necessary to perform simultaneous firing of the dielectric layer and the internal electrode layer in a reducing atmosphere. is there. But,
When firing in a reducing atmosphere, the dielectric layer is reduced and the specific resistance becomes low. Therefore, non-reducing dielectric materials have been developed.

The capacitor is also required to have good temperature characteristics, and in particular, depending on the application, it is required to have flat temperature characteristics under severe conditions. recent years,
Multilayer ceramic capacitors have come to be used in various electronic devices such as an engine electronic control unit (ECU), a crank angle sensor, and an antilock brake system (ABS) module mounted in an engine room of an automobile. Since these electronic devices are for stably performing engine control, drive control, and brake control, it is required that the circuit has good temperature stability.

In the environment where these electronic devices are used, it is expected that the temperature will drop to about -20 ° C or lower in the winter in a cold region, and will rise to + 130 ° C or higher in the summer after the engine is started. To be done. Recently, there is a tendency to reduce a wire harness that connects an electronic device and a device to be controlled, and since the electronic device may be installed outside the vehicle, the environment for the electronic device is becoming more and more severe. Therefore, the capacitors used in these electronic devices need to have flat temperature characteristics in a wide temperature range.

Temperature compensating capacitor material with excellent temperature characteristics
As the material, (Sr, Ca) (Ti, Zr) O_Threesystem,
Ca (Ti, Zr) O_ThreeSystem, Nd_TwoO_Three-2Ti
O_Two System, La_TwoO_Three-2 TiO_TwoThe system is generally known
However, these compositions have a very low dielectric constant.
(Generally 100 or less)
Is virtually impossible to make.

As a dielectric ceramic composition having a high dielectric constant and a flat capacitance-temperature characteristic, BaTiO ₃ is the main component, Nb ₂ O ₅ —Co ₃ O ₄ , MgO—Y, rare earth elements (Dy, Ho, etc.). ), Bi ₂ O ₃ —TiO
A composition containing _{2 and the} like is known. These BaT
The temperature characteristics of the dielectric ceramic composition containing iO ₃ as the main component are such that the Curie temperature of BaTiO ₃ is around 130 ° C., so the R-characteristics of the capacity-temperature characteristics (ΔC = ± 15% or less) in the higher temperature region. ) Is very difficult to satisfy. Therefore, the BaTiO ₃ -based high dielectric constant material is E
IA standard X7R characteristics (-55 to 125 ° C, ΔC = ± 1
Only within 5%). Merely satisfying the X7R characteristics cannot meet the electronic equipment of automobiles used in the above severe environment. The electronic device has an EIA standard X8R characteristic (-55 to 150 ° C., ΔC
= ± 15% or less) is required.

BaTiO_ThreeDielectric porcelain mainly composed of
In order to satisfy the X8R characteristic in the composition, BaT
iO_ThreeBy replacing Ba in the inside with Bi, Pb, etc.
Therefore, it is suggested to shift the Curie temperature to the high temperature side.
(Japanese Patent Application Laid-Open No. 10-25157, 9-40).
465). In addition, BaTiO 3_Three+ CaZrO
_Three+ ZnO + Nb_TwoO₅Selecting the composition of the system
It is also proposed to satisfy X8R characteristics by
(JP-A-4-295048, JP-A-4-292458)
No. 4,292,459 and No. 5-10931.
9 gazette and the same 6-243721 gazette). But these
In any composition system of Pb,
Since Bi and Zn are used, in an oxidizing atmosphere such as air
Is premised on firing. Therefore, the internal electrodes of the capacitor
Inexpensive base metals such as Ni cannot be used for
expensive precious metals such as d, Au, Ag must be used
There is a problem that there is no.

Further, the conventional dielectric ceramic composition has a problem that it cannot cope with repeated thermal shock from a low temperature to a high temperature, and improvement in mechanical strength is required.

On the other hand, a method has been reported in which the strength is increased by forming needle crystals in the outer surface regions at both ends of the ceramic laminate in the laminating direction (Japanese Patent Laid-Open No. 9-3.
12234). In the method shown in this publication, TiO 2
_The oxide paste containing ₂ as a main component is applied to the surface of the ceramic laminate, dried and then heat-treated to form needle crystals in the outer surface region of the ceramic. The acicular crystals are Ba ₄ Ti ₁₃ O ₃₀ and Ba ₆ Ti ₁₇ O.
It is considered to be a precipitate such as ₄₀ .

[0012]

However, in the method described in the above publication, when the ceramic laminate is fired in a reducing atmosphere, the ceramic base is reduced, so that the inside of the ceramic laminate or the vicinity thereof is It is not possible to form needle crystals. Therefore, the formation of needle-like crystals is limited only to the vicinity of the outer surface of the ceramic laminate, and the mechanical strength is not sufficiently improved. Therefore, when the thickness of the capacitor lid for protecting the ceramic laminate is not sufficient, it is not possible to obtain an electronic component having sufficient strength for practical use.

An object of the present invention is that the dielectric constant is high and the capacitance-temperature characteristic is the X8R characteristic (-55 to 150 ° C., which is EIA standard).
ΔC = ± 15% or less), capable of firing in a reducing atmosphere, and providing a dielectric ceramic composition having excellent mechanical strength. An object is to provide an electronic component such as a monolithic ceramic capacitor using a product.

[0014]

In order to achieve the above object, the dielectric ceramic composition according to the first aspect of the present invention comprises BaTiO _{3 as} a main component, MgO, CaO, and Ba.
A first subcomponent containing at least one selected from O, SrO and Cr ₂ O ₃ , and (Ba, Ca) _x Si
_Second subcomponent represented by O _{2 + x} (where x = 0.8 to 1.2), V ₂ O ₅ , MoO ₃ and WO
_{A third} subcomponent containing at least one selected from ₃ , a fourth subcomponent containing an oxide of R1 (provided that R1 is Yb), and an oxide of R2 (provided that R2 is Y, Dy, H).
BaTiO ₃ 100 which is a dielectric ceramic composition having at least a fifth subcomponent containing at least one selected from o, Tb, Gd and Eu, and which is the main component.
The ratio of each subcomponent to the moles is as follows: first subcomponent: 0.1 to 3 mol, second subcomponent: 2 to 10 mol, third subcomponent: 0.01 to 0.5 mol, fourth subcomponent: 0.5 to 7 mol (however, the number of moles of the fourth subcomponent is the ratio of R1 alone), the fifth subcomponent: 2 to 9 mol (however, the number of moles of the fifth subcomponent is R2 alone). Is the ratio), and is characterized by. In the second subcomponent, the ratio of Ba and Ca is arbitrary, and only one may be contained.

Preferably, the dielectric ceramic composition according to the present invention further contains MnO as a sixth subcomponent, and the content of the sixth subcomponent is BaTiO ₃ 10 which is the main component.
It is 0.5 mol or less relative to 0 mol.

Preferably, the total content of the fourth subcomponent and the fifth subcomponent is BaTiO ₃ 1 which is the main component.
It is 13 mol or less with respect to 00 mol (however, the number of moles of the fourth subcomponent and the fifth subcomponent is the ratio of R1 and R2 alone).

A dielectric ceramic composition according to a second aspect of the present invention comprises a dielectric matrix phase containing BaTiO ₃ as a main component,
It has a plate-like or needle-like precipitation phase mixed inside the dielectric matrix phase. In the dielectric ceramic composition according to the second aspect of the present invention, the material of the precipitation phase is not particularly limited, but is composed of, for example, a composite oxide of Y, Yb, and Ti.

The electronic component according to the present invention is not particularly limited as long as it is an electronic component having a dielectric layer. For example, a laminated ceramic having a capacitor element body in which dielectric layers and internal electrode layers are alternately laminated. It is a capacitor element. In the present invention, the dielectric layer is composed of any one of the above dielectric compositions. The conductive material contained in the internal electrode layer is not particularly limited, but may be Ni or N, for example.
It is an i alloy.

[0019]

According to the present invention, X8R (-55 to 150 ° C,
(ΔC = ± 15% or less) A dielectric ceramic composition that satisfies temperature characteristics, is excellent in reduction resistance, and is excellent in mechanical strength can be obtained.

In the present invention, the ratio of R2 to 100 mol of BaTiO ₃ is 2 mol or more, and the composite addition with R1 sufficiently improves the mechanical strength. Such new knowledge was first discovered by the present inventors.

When the ratio of R1 is less than 0.5 mol, it tends to be difficult to obtain X8R characteristics, and the composition of R2 exceeds 9 mol or the oxide of R1 exceeds 7 mol. When added to the product, the sinterability deteriorates,
At the same time that good electrical characteristics cannot be obtained, sufficient mechanical strength tends to be lost.

Further, according to the present invention, the dielectric ceramic composition in which a plate-shaped or needle-shaped precipitation phase is detected inside the dielectric matrix phase is compared to a dielectric ceramic composition in which these precipitation phases are not detected. Thus, an increase in mechanical strength is observed.

Further, the dielectric ceramic composition according to the present invention is
It can be fired in a reducing atmosphere and can be used as a material for a laminated chip capacitor having internal electrodes made of a base metal such as Ni and a Ni alloy.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below based on the embodiments shown in the drawings. 1 is a cross-sectional view of a monolithic ceramic capacitor according to an embodiment of the present invention, FIG. 2A is a SEM photograph (backscattered electron image) of a dielectric ceramic composition according to an embodiment of the present invention, and FIG. 3) is a SEM photograph (reflected electron image) of a dielectric ceramic composition according to a comparative example of the present invention, FIG.
(A) is an SEM photograph (backscattered electron image) of a dielectric ceramic composition according to another embodiment of the present invention, and FIG. 3B is a SEM photograph of a dielectric ceramic composition according to another comparative example of the present invention. (Reflected electron image), FIGS. 4A and 4B are SEM photographs (secondary electron images) of dielectric ceramic compositions according to other examples of the present invention.

Multilayer Ceramic Capacitor As shown in FIG. 1, a monolithic ceramic capacitor 1 according to an embodiment of the present invention includes a dielectric layer 2 and an internal electrode layer 3.
The capacitor element body 10 has a structure in which and are alternately stacked. At both ends of the capacitor element body 10, a pair of external electrodes 4 is 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 usually a rectangular parallelepiped. The size is not particularly limited, and may be an appropriate size depending on the application, but usually (0.6
~ 5.6 mm) x (0.3 to 5.0 mm) x (0.3 to
1.9 mm).

The internal electrode layers 3 are laminated so that the respective end faces are alternately exposed on the surfaces of the two opposite end portions of the capacitor element body 10. The pair of external electrodes 4 are formed at both ends of the capacitor element body 10 and are 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 of the present invention.
The dielectric ceramic composition of the present invention is composed of BaTiO 3 which is the main component.
₃ and MgO, CaO, BaO, SrO and Cr
_A first subcomponent containing at least one selected from ₂ O ₃ and (Ba, Ca) _x SiO _{2 + x} (provided that
x = 0.8 to 1.2) and V ₂
A third subcomponent containing at least one selected from O ₅ , MoO ₃ and WO ₃ , a fourth subcomponent containing an oxide of R1 (where R1 is Yb), and an oxide of R2 (providing R2). Is Y, Dy, Ho, Tb, Gd and E
and a dielectric porcelain composition having at least a fifth sub ingredient including at least one selected from u).

The ratio of each of the above subcomponents to BaTiO _{3 as the} main component is such that the first subcomponent: 0.1 to 3 mol, the second subcomponent: 2 to 10 mol, and the third subcomponent to 100 mol of BaTiO _3. Component: 0.01 to 0.5 mol, Fourth subcomponent: 0.5 to 7 mol, Fifth subcomponent: 2 to 9 mol, preferably First subcomponent: 0.5 to 2.5. Mol, second subcomponent: 2.0 to 5.0 mol, third subcomponent: 0.1 to 0.4 mol, fourth subcomponent: 0.5 to 5.0 mol, fifth subcomponent: 2 ~ 8 moles. The ratios of the fourth subcomponent and the fifth subcomponent are not the molar ratio of the oxide of R1 and the oxide of R2, but the molar ratio of R1 alone and the molar ratio of R2 alone.
That is, when using an oxide of Yb as the fourth subcomponent, the ratio of the fourth subcomponent being 1 mole, Yb ₂
It does not mean that the ratio of O ₃ is 1 mol, but that the ratio of Yb is 1 mol.

In the present specification, each oxide constituting the main component and each subcomponent is represented by the stoichiometric composition, but the oxidation state of each oxide may be out of the stoichiometric composition. Good. However, the above-mentioned ratio of each sub-component is calculated by converting the amount of metal contained in the oxide constituting each sub-component into the oxide of the above stoichiometric composition.

The reasons for limiting the contents of the above subcomponents are as follows. First subcomponent (MgO, CaO, BaO,
If the contents of SrO and Cr ₂ O ₃ ) are too small, the rate of change in capacity with temperature becomes large. On the other hand, if the content is too large, the sinterability deteriorates. The composition ratio of each oxide in the first subcomponent is arbitrary.

Second subcomponent [(Ba, Ca)_xSiO
_{2 + x}] Contained BaO and CaO in the first subcomponent.
However, it is a complex oxide (Ba, Ca)_xSiO
_{2 + x} Has a low melting point and therefore has good reactivity with the main component
Therefore, in the present invention, BaO and / or CaO is added to the above
It is also added as a compound oxide. Low content of second subcomponent
If too much, the capacity-temperature characteristic deteriorates, and IR (insulation
Resistance) decreases. On the other hand, if the content is too high, the dielectric constant
Will cause a sharp drop in. (Ba, Ca) _xSi
O_{2 + x}X in is preferably 0.8 to 1.2
Yes, and more preferably 0.9 to 1.1. x is small
Too much, ie SiO_TwoToo much of the main component
BaTiO_ThreeReact with and deteriorate the dielectric properties.
U On the other hand, if x is too large, the melting point becomes high and the sinterability increases.
It is not preferable because it worsens. In addition, in the second subcomponent
The ratio of Ba to Ca is arbitrary and only one of them is included.
You may have.

The third subcomponent (V ₂ O ₅ , MoO ₃ and WO ₃ ) has the effect of flattening the capacity-temperature characteristic above the Curie temperature. If the content of the third sub ingredient is too small, such an effect becomes insufficient. On the other hand, if the content is too large, the IR is significantly reduced. The composition ratio of each oxide in the third subcomponent is arbitrary.

The fourth subcomponent (oxide of R1) exhibits the effect of shifting the Curie temperature to the high temperature side and the effect of flattening the capacity-temperature characteristic. If the content of the fourth subcomponent is too small, such effects become insufficient and the capacity-temperature characteristic deteriorates. On the other hand, if the content is too large, the sinterability tends to deteriorate. Among the fourth subcomponents, Yb oxide is preferable because it has a high property improving effect and is inexpensive.

By adding the fifth subcomponent (oxide of R2) together with the fourth subcomponent (oxide of R1), the mechanical strength of the obtained dielectric ceramic composition is sufficiently improved. Also,
The fifth subcomponent has the effect of improving IR and has little adverse effect on the capacity-temperature characteristic. However, if the content of the oxide of R2 is too large, the sinterability tends to deteriorate. Among the fifth subcomponents, the Y oxide is preferable because it has a high property improving effect and is inexpensive.

The total content of the fourth subcomponent and the fifth subcomponent is preferably 13 mol or less with respect to 100 mol of BaTiO _{3 as} the main component (however, the fourth subcomponent and the fifth subcomponent).
The number of moles of the subcomponent is the ratio of R1 and R2 alone). This is for maintaining good sinterability.

The dielectric ceramic composition of the present invention may further contain MnO as a sixth subcomponent. The sixth subcomponent has the effect of promoting sintering and the effect of increasing IR. In order to obtain such an effect sufficiently, it is preferable that the ratio of the sixth subcomponent with respect to 100 mol of BaTiO ₃ is 0.01 mol or more. However, if the content of the sixth subcomponent is too large, the capacity-temperature characteristic is adversely affected, so the content is preferably 0.5 mol or less.

Further, in the dielectric ceramic composition of the present invention,
In addition to the above oxides, Al_TwoO_Three May be included
Yes. Al_TwoO_ThreeInfluences the capacity-temperature characteristics too much
However, the effect of improving sinterability and IR is exhibited. However, Al
_TwoO_ThreeIf the content of is too large, the sinterability deteriorates and the IR
Lowers Al_TwoO_ThreeIs preferably Ba
TiO_Three1 mol or less, more preferably 100 mol
Preferably, it is 1 mol or less based on the total amount of the dielectric ceramic composition.

At least one of Sr, Zr and Sn is Ba in the main component forming the perovskite structure.
Alternatively, when Ti is substituted, the Curie temperature shifts to the low temperature side, and the capacity-temperature characteristic at 125 ° C. or higher deteriorates. Therefore, BaTiO ₃ containing these elements
[For example, (Ba, Sr) TiO ₃ ] is preferably not used 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 entire dielectric ceramic composition).

The average crystal grain size of the dielectric ceramic composition of the present invention is not particularly limited, and may be appropriately determined from the range of 0.1 to 3.0 μm, for example, depending on the thickness of the dielectric layer.
The capacitance-temperature characteristics tend to deteriorate as the dielectric layer becomes thinner, and as the average crystal grain size becomes smaller. Therefore, the dielectric ceramic composition of the present invention is particularly effective when it is necessary to reduce the average crystal grain size, specifically, when the average crystal grain size is 0.1 to 0.5 μm. is there. Further, if the average crystal grain size is made small, the IR accelerated life becomes long, and the change with time of the capacity under a DC electric field is reduced. Therefore, from this point as well, the average crystal grain size is small as described above. preferable.

The Curie temperature (phase transition temperature from ferroelectric to paraelectric) of the dielectric ceramic composition of the present invention can be changed by selecting the composition, but in order to satisfy the X8R characteristic. Is preferably 120 ° C. or higher, more preferably 123 ° C. or higher. The Curie temperature is
It can be measured by DSC (differential scanning calorimetry) or the like.

The thickness of the dielectric layer composed of the dielectric ceramic composition of the present invention is usually 40 μm or less per layer,
In particular, it is 30 μm or less. The lower limit of thickness is usually 2 μm
It is a degree. The dielectric ceramic composition of the present invention is effective in improving the capacitance-temperature characteristic of a laminated ceramic capacitor having such a thinned dielectric layer. The number of laminated dielectric layers is usually about 2 to 300.

However, the composition of the present invention is effective in improving the strength characteristics without depending on the design of the multilayer chip capacitor.

A laminated ceramic capacitor using the dielectric ceramic composition of the present invention has a temperature of 80 ° C. or higher, particularly 125 to 15
It is suitable for use as an electronic component for equipment used in an environment of 0 ° C. Then, in such a temperature range, the temperature characteristic of the capacity satisfies the R characteristic of the EIA standard, and further,
The X8R characteristic is also satisfied. In addition, the B characteristic of the EIAJ standard [capacity change rate within ± 10% at −25 to 85 ° C. (reference temperature 20 ° C.)] and the X7R characteristic of the EIA standard (−55 to 125
(° C, ΔC = within ± 15%) can be satisfied at the same time.

In the monolithic ceramic capacitor, the dielectric layer usually has a thickness of 0.02 V / μm or more, especially 0.2 V / μm.
Above, more than 0.5V / μm, generally 5V / μm
An AC electric field of about less than or equal to that and a DC electric field of 5 V / μm or less superimposed on it are applied, but even if such an electric field is applied, the temperature characteristic of the capacitance is extremely stable.

The dielectric magnetic composition of the present invention has the composition range as described above, and BaTiO 3 is contained in the element body after firing.
_It has a dielectric matrix phase containing ₃ as a main component, and a plate-like or acicular precipitation phase mixed inside the dielectric matrix phase.

As described above, the dielectric ceramic composition in which the plate-shaped or needle-shaped precipitation phase is detected inside the dielectric matrix phase satisfies the X8R characteristic and, at the same time, does not detect these precipitation phases. Particularly improved mechanical strength is observed compared to the porcelain composition.

Besides the above composition range, a dielectric ceramic composition in which a plate-shaped or needle-shaped precipitation phase is detected inside the dielectric matrix phase is also within the scope of the present invention.

Internal Electrode Layer 3 The conductive material contained in the internal electrode layer 3 is not particularly limited, but since the constituent material of the dielectric layer 2 has reduction resistance, a base metal can be used. As the base metal used as the conductive material, Ni or Ni alloy is preferable. The Ni alloy is selected from Mn, Cr, Co and Al 1
An alloy of one or more elements and Ni is preferable, and Ni in the alloy is
The content is preferably 95% by weight or more. In addition,
In Ni or Ni alloy, various trace components such as P are less than 0.1%.
It may be contained in an amount of about 1% by weight or less. The thickness of the internal electrode layer may be appropriately determined according to the application, etc., but is usually 0.
The thickness is preferably 5 to 5 μm, and more preferably 0.5 to 2.5 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 alloys of these can be used. The thickness of the external electrode may be appropriately determined according to the application, etc., but is usually preferably about 10 to 50 μm.

Manufacturing Method of Multilayer Ceramic Capacitor A multilayer ceramic capacitor using the dielectric ceramic composition of the present invention is the same as a conventional multilayer ceramic capacitor.
It is manufactured by producing a green chip by a usual printing method or a sheet method using a paste, firing this, and then printing or transferring an external electrode and firing it. Less than,
The manufacturing method will be specifically described.

The dielectric layer paste may be either an organic paint prepared by kneading a dielectric material and an organic vehicle, or an aqueous paint.

As the dielectric raw material, the above-mentioned oxides, mixtures thereof, and complex oxides can be used. In addition, various compounds such as carbonates and shu, which become the above-mentioned oxides and complex oxides by firing. Acid salts, nitrates, hydroxides,
It can be appropriately selected from organometallic compounds and the like and mixed and used. The content of each compound in the dielectric material may be determined so as to have the above-mentioned composition of the dielectric ceramic composition after firing. The dielectric material usually has an average particle size of 0.1 to 3 μm.
It is used as a powder of about m.

The organic vehicle is a binder dissolved 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. The organic solvent used is also not particularly limited, and may be appropriately selected from various organic solvents such as terpineol, butyl carbitol, acetone, and toluene according to the method to be used such as the printing method and the sheet method.

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

The internal electrode layer paste contains a conductive material made of the above-mentioned various dielectric metals or alloys, or various oxides, organometallic compounds, resinates, etc., which become the above-mentioned conductive material after firing, and the above-mentioned organic vehicle. Prepare by kneading. The external electrode paste may be prepared in the same manner as the above internal electrode layer paste.

The content of the organic vehicle in each of the above-mentioned pastes is not particularly limited, and the usual content may be, for example, about 1 to 5% by weight of the binder and about 10 to 50% by weight of the solvent. In addition, each paste may contain additives selected from various dispersants, plasticizers, dielectrics, insulators and the like, if necessary. The total content of these is 1
It is preferably 0% by weight or less.

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 peeled from the substrate to obtain a green chip.

When the sheet method is used, a dielectric layer paste is used to form a green sheet, an internal electrode layer paste is printed on the green sheet, and these are stacked to form a green chip.

Before firing, the green chip is subjected to binder removal processing. The binder removal treatment may be performed under normal conditions, but when a base metal such as Ni or a Ni alloy is used for the conductive material of the internal electrode layers, it is particularly preferably performed under the following conditions. Temperature rising rate: 5 to 300 ° C / hour, especially 10 to 100 ° C /
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 for firing the green chip may be appropriately determined according to the type of the conductive material in the internal electrode layer paste, but when a base metal such as Ni or Ni alloy is used as the conductive material, the firing atmosphere is Oxygen partial pressure of 10 ^-8 to 1
The pressure is preferably ^0-15 atm. If the oxygen partial pressure is less than the above range, the conductive material of the internal electrode layers may abnormally sinter and be interrupted. When the oxygen partial pressure exceeds the above range, the internal electrode layers tend to be oxidized.

The holding temperature during firing is preferably 1
100-1400 ° C, more preferably 1200-136
The temperature is 0 ° C, more preferably 1200 to 1320 ° C.
If the holding temperature is less than the above range, the densification becomes insufficient, and if it exceeds the above range, the electrode is discontinued due to abnormal sintering of the internal electrode layer, and the capacity-temperature characteristic is deteriorated due to the diffusion of the internal electrode layer constituent material, and the dielectric Reduction of the body porcelain composition is likely to occur.

Various conditions other than the above conditions are preferably selected from the following range. Temperature rising rate: 50 to 500 ° C./hour, especially 200 to 300
° 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. The firing atmosphere is preferably a reducing atmosphere, and 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 lifetime and thus improve reliability.

The oxygen partial pressure in the annealing atmosphere is 10 ^−9.
It is preferable that the pressure is not less than atmospheric pressure, particularly 10 ⁻⁶ to 10 ⁻⁹ atmospheric pressure. If the oxygen partial pressure is less than the above range, it is difficult to reoxidize the dielectric layer, and if it exceeds the above range, the internal electrode layers tend to be oxidized.

The holding temperature during annealing is preferably 1100 ° C. or lower, and particularly preferably 500 to 1100 ° C. If the holding temperature is less than the above range, the dielectric layer is not sufficiently oxidized, so that the IR is low and the IR life is apt to be shortened. On the other hand, if the holding temperature exceeds the above range, not only the internal electrode layer is oxidized and the capacitance is lowered, but also the internal electrode layer reacts with the dielectric substrate, which deteriorates the capacitance-temperature characteristic, I
R and IR life are likely to decrease. It should be noted that the annealing may be composed only of a temperature raising process and a temperature lowering process. That is, the temperature holding time may be zero. In this case, the holding temperature is synonymous with the maximum temperature.

Various conditions other than the above conditions are preferably selected from the following range. Temperature holding time: 0 to 20 hours, especially 6 to 10 hours, cooling rate: 50 to 500 ° 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 binder removal processing, firing and annealing, for example, a wetter or the like may be used to wet the N ₂ gas, the mixed gas and the like. in this case,
The water temperature is preferably about 5 to 75 ° C.

The binder removal processing, firing and annealing are
It may be carried out continuously or independently. When performing these continuously, after the binder removal treatment, the atmosphere was changed without cooling, the temperature was raised to the holding temperature during firing, firing was performed, and then cooling was performed to reach the holding temperature for annealing. It is sometimes preferable to change the atmosphere and perform annealing. On the other hand, in the case of performing these independently, during firing, after raising the temperature to the holding temperature at the time of binder removal treatment in an atmosphere of N ₂ gas or humidified N ₂ gas, the atmosphere is changed and the temperature is further continued. After cooling to the holding temperature at the time of annealing, it is preferable to change to N ₂ gas or humidified N ₂ gas atmosphere again and continue cooling. When annealing, N ₂
After raising the temperature to the holding temperature in a gas atmosphere, the atmosphere may be changed, or the entire annealing process may be performed in a humidified N ₂ gas atmosphere.

The capacitor element body obtained as described above is subjected to end face polishing by, for example, barrel polishing or sandblasting, and the external electrode paste is printed or transferred and baked to form the external electrodes 4. The firing conditions for the external electrode paste are preferably, for example, about 10 minutes to 1 hour at 600 to 800 ° C. in a wet 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 monolithic ceramic capacitor of the present invention thus manufactured is mounted on a printed circuit board or the like by soldering,
Used in various electronic devices.

The present invention is not limited to the above-mentioned embodiment, but can be variously modified within the scope of the present invention.

For example, in the above-described embodiment, the laminated ceramic capacitor is exemplified as the electronic component according to the present invention, but the electronic component according to the present invention is not limited to the laminated ceramic capacitor, and the dielectric ceramic composition having the above composition is used. Any material may be used as long as it has a dielectric layer made of a material.

[0072]

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

[0073]Examples 1-9 and Comparative Examples 1-4 (Production of prismatic dielectric sample) Particle size of 0.1 to 1 μm
BaTiO_Three, MgCO_Three, MnCO_Three, (Ba
_0.6Ca_0.4) SiO_Three, V_TwoO₅, R
Material powder selected from oxide of 1 and oxide of R2
By wet mixing at 16 o'clock with a rumill and drying
Dielectric material was used. The composition of the dielectric material is powder of these materials.
A plurality of dielectric materials were prepared by changing the mixing ratio of.

In this embodiment, BaTiO 3 is used._Three  100m
Yb as a fourth subcomponent (oxide of R1) with respect to ol
_TwoO_ThreeAs a fifth subcomponent (oxide of R2)
Y_Two O_ThreeAnd the other additives are listed in Table 1.
Weigh it to the desired amount, wet mix with a ball mill,
It was dried to obtain a dielectric material.

BaTiO ₃ is produced by the hydrothermal synthetic powder method,
Alternatively, similar characteristics were obtained by using a raw material prepared by the oxalate method or the like.

To the above dielectric material, polyvinyl alcohol as a binder was added in an amount of 0.05% by weight, and the binder and the dielectric composition were mixed so as to form a granule. 3 g of the above-mentioned granular dielectric composition was weighed, length 35 mm, length 5
mm and width 5 mm were pressed into a rod shape. This molded body is baked at a temperature of 300 ° C./hour and a holding temperature of 800.
The binder removal treatment was performed under conditions of a temperature of 2 ° C., a holding time of 2 hours, and an atmosphere of air and a humidified nitrogen gas (1 × 10 ⁻⁵ atm).

Then, the molded body was heated at a heating rate of 200 ° C.
/ Hour 1280 ~ 1370 ℃, holding time 2 hours,
Firing is performed at a cooling rate of 300 ° C./hour under a mixed gas atmosphere of humidified nitrogen gas and hydrogen gas (1 × 10 ⁻⁹ atm) to obtain a fired body having a length of about 30 mm and a length and width of about 4.5 mm. It was The fired body was annealed under the conditions of a holding time of 900 ° C., a holding time of 9 hours, a cooling rate of 300 ° C./hour, and a humidified nitrogen gas atmosphere (1 × 10 ⁻⁵ atm). A wetter was used to humidify each atmosphere gas, and the water temperature was set to 35 ° C.

The prismatic ceramics sintered body sample thus obtained was mirror-polished to a length of 35 mm, a length of 3 mm, and a width of 3 mm. This was used as a sample for bending strength measurement. The bending strength of the sample thus obtained was measured by the three-point bending method. The results are shown in Table 1.

For the dielectric ceramic characteristics, the density of the sintered body was calculated from the dimensions and mass of the prismatic sample which was molded and fired into a prismatic shape, and the sinterability was evaluated from this result. The sintered body density is shown in Table 1.

With respect to the obtained prismatic ceramics sintered body sample, a powder X-ray (Cu-Kα ray) diffractometer was used to measure 2θ = 29 ° to 32 ° under the following conditions:
The presence or absence of a precipitation phase was confirmed and identified. X-ray generation condition: 45 kV-40 mA, scan width: 0.01 °, scan speed: 0.2 ° / min, X-ray detection condition, parallel slit: 0.5 °, divergence slit: 0.5 °, light receiving slit : 0.15 mm. The results are shown in Table 1.

Further, with respect to the obtained prismatic ceramics sintered body samples, SEM photographs were taken to confirm the presence or absence of plate-like or needle-like precipitates.

The specific resistance at 25 ° C. of the obtained prismatic ceramics sintered body sample was measured. Insulation resistance meter (R manufactured by Advantest Co., Ltd.)
8340A (50V-1 minute value)). The results are shown in Table 1.

(Production of Multilayer Ceramic Capacitor) For the dielectric paste, 100% by weight of each dielectric material is used.
Acrylic resin 4.8% by weight, methylene chloride 40% by weight, ethyl acetate 20% by weight, mineral spirits 6% by weight, and acetone 4% by weight were mixed in a ball mill to form a paste.

Regarding the internal electrode paste, 100% by weight of nickel particles having an average particle diameter of 0.2 to 0.8 μm,
40% by weight of organic vehicle (8% by weight of ethylene cellulose resin dissolved in 92% by weight of butyl carbitol)
And 10% by weight of butyl carbitol were kneaded with a three-roll to form a paste.

As for the external electrode paste, 100% by weight of copper particles having an average particle size of 0.5 μm and an organic vehicle (8% by weight of ethylene cellulose resin and butyl carbitol 92) were used.
35% by weight) (dissolved in 1% by weight) and 7% by weight of butyl carbitol were kneaded with a triple roll to form a paste.

Next, a 15 μm-thick green sheet was formed on a PET film using the above-mentioned dielectric paste, and the internal electrode paste was printed on the green sheet.
The green sheet was peeled from the film. The green sheets thus obtained were laminated and pressure-bonded to produce a green chip. The number of stacked green sheets having internal electrodes was five.

This green chip was cut into a predetermined size and subjected to binder removal processing, firing and annealing to obtain a laminated ceramic fired body. The size of each fired sample is 3.2 m
m × 1.6 mm × 0.6 mm, the thickness of the dielectric layer was about 10 μm, and the thickness of the internal electrode was 2 μm.

Next, after polishing the end faces of this laminated ceramic fired body by sandblasting, the external electrode paste was transferred to the end faces and fired at 800 ° C. for 10 minutes in a humidified nitrogen gas and hydrogen gas atmosphere. External electrodes were formed to obtain a multilayer ceramic capacitor sample.

The binder removal processing was performed under the following conditions. Temperature rising rate: 15 ° C / hour, holding temperature: 280 ° C, temperature holding time: 8 hours, atmosphere: air.

The firing was performed under the following conditions. Temperature rising rate: 200 ° C./hour, holding temperature: 1200 to 1300 ° C., temperature holding time: 2 hours, cooling rate: 300 ° C./hour, firing atmosphere: using a mixed gas of humidified N ₂ and H ₂ , oxygen ^Partial pressure: ^10-11 atm.

Annealing was performed under the following conditions. Holding temperature: 900 ° C., temperature holding time: 9 hours, cooling rate: 300 ° C./hour, annealing atmosphere: using humidified N ₂ gas, oxygen partial pressure: 10 ⁻⁷ atm.

With respect to the multilayer ceramic capacitor sample thus obtained, the relative permittivity (εr), the dielectric loss (tan δ) and the capacitance-temperature characteristic were measured. With respect to the multilayer ceramic capacitor, the capacitance and the dielectric loss (tan δ) under the conditions of 1 KHz and 1 Vrms were measured using an LCR meter. From the obtained capacitance, electrode dimensions and distance between electrodes, the relative permittivity (εr)
Was calculated.

Regarding the temperature characteristic of the capacitance, the laminated ceramic capacitor sample was measured with an LCR meter at -55.
The capacitance was measured at a voltage of 1 V in the temperature range of ℃ to 160 ℃, and the rate of change in capacity when the reference temperature was 25 ℃ was within ± 15% within the range of -55 ℃ to 125 ℃. EIA standard X7R) shall satisfy the X7R temperature characteristics, and shall be within ± 55 ° C to 150 ° C.
Those within 15% (X8R of the EIA standard of the Japan Electro-Mechanical Industry Association) were considered to satisfy the X8R temperature characteristics, and when satisfied, were evaluated as “◯”, and when not satisfied, were evaluated as “×”.

[0094]

[Table 1]

(Evaluation) As shown in Table 1, as compared with Comparative Examples 1 to 4 which are out of the composition range of the present invention, in Examples 1 to 9 in the composition range of the present invention, the bending strength is 10 kgf / mm
^{It was 2} , which was confirmed to be sufficiently high. In addition, in the compositions of Examples 1 to 9, plate-shaped or needle-shaped precipitation phases appeared in the dielectric matrix phase, and in comparison with the compositions of Comparative Examples 1 to 4 in which plate-shaped or needle-shaped precipitation did not occur, bending was observed. It was also confirmed that the strength was improved. This precipitation phase is considered to be an oxide mainly composed of rare earth and Ti. Even in Examples 1 to 9, the bending strength was 10 kgf / mm depending on the sintering temperature.
^Although it may be lower than ² , adequate bending strength can be provided by appropriately setting the sintering temperature.

Further, in the composition range of Examples 1 to 9, the reduction-resistant dielectric composition was not reduced even when fired in a reducing atmosphere, and the nickel used as the internal electrode was not oxidized. It was also confirmed that the product was obtained and satisfied the X8R temperature characteristics. In addition, in the composition range of Examples 1 to 9, the sintered density was 5.15 mg / mm ³ or more, and it was confirmed that the sinterability was also good. In addition, also in Examples 1 to 9, depending on the sintering temperature, the sintered density was 5.
Although it may not be 15 mg / mm ³ or more, it is possible to provide sufficient sinterability by appropriately setting the sintering temperature.

Further, in the composition range of Examples 1 to 9, the dielectric loss (tan δ) was within 5% and the specific resistance was 1E +.
It was confirmed that it was 11 or more, and the characteristics as a capacitor were excellent. Even in Examples 1 to 9, depending on the sintering temperature, these conditions may not be satisfied,
By properly setting the sintering temperature, good dielectric loss and specific resistance can be provided.

Examples 10 to 14 and Comparative Examples 5 to 7 With respect to 100 mol of BaTiO ₃ , the fourth subcomponent (R
Yb is added as a composition amount of 4.3 mol, and Eu, Gd, Tb, Dy, Ho, Nb, Ta, Sm are added as a fifth subcomponent (oxide of R2).
Was added in a composition amount of 2 mol as an element ratio, and the other additives were blended in the amounts shown in Table 2, in the same manner as in Examples 1 to 9 A sample and a laminated ceramic capacitor sample were prepared. Table 2 shows the results obtained by measuring various characteristics of these samples in the same manner as in Examples 1 to 9.

[0099]

[Table 2]

(Evaluation) As shown in Table 2, as compared with Comparative Example 1 in Table 1 in which the fifth subcomponent (oxide of R2) was not added, Ho, Y, Dy, Eu, Gd and Tb were added. It was confirmed that in Examples 10 to 14, the bending strength was improved. Comparative Example 5 in which Nb, Ta, and Sm out of the composition range of the present invention were added as the fifth subcomponent (oxide of R2)
To 7, within the composition range of the present invention, Ho, Y, Dy,
In the case of Examples 10 to 14 in which Eu, Gd and Tb were added,
It was confirmed that the bending strength was improved. Also, in the case of Examples 10 to 14, it was confirmed that the X8R temperature characteristics were satisfied. Further, it was confirmed that even in the composition ranges of Examples 10 to 14, the dielectric loss (tan δ) was within 5%, the specific resistance was 1E + 11 or more, and the characteristics as a capacitor were excellent.

Example 15 and Comparative Example 8 The dielectric ceramic composition was as shown in Table 3, the thickness of the dielectric layer was 16 μm, the number of dielectric layers was 46, and the size of each capacitor sample was 3. 2 mm x 1.6 mm x 1.0
A multilayer ceramic capacitor sample was prepared in the same manner as in Examples 1 to 9 except that the thickness was set to mm.

Table 3 shows the results of measuring various characteristics of these capacitor samples in the same manner as in Examples 1-9. For the bending strength measurement of the capacitor sample by the three-point bending method, one having no external electrode was used.

[0103]

[Table 3]

(Evaluation) As shown in Table 3, it was confirmed that the laminated capacitor sample having the composition according to Example 15 also has improved bending strength as compared with the capacitor sample having the composition according to Comparative Example 8. did it. Further, it was confirmed that the reduction-resistant dielectric composition was obtained without being reduced even by firing in a reducing atmosphere and without oxidizing the nickel used as the internal electrode. It was also confirmed that the case of Example 15 also satisfied the X8R temperature characteristics.

Example 16 Yb in the fourth subcomponent (oxide of R1) was 6.00 mol%.
In the same manner as in Example 1, except that the mol% of Y in the fifth subcomponent (oxide of R2) was 4.00 mol% and the sintering temperature was 1325 ° C. A bound sample was prepared.

A SEM photograph of the sample is shown in FIG. The SEM photograph was photographed by using a scanning electron microscope (SEM: product number JSM-T300 manufactured by JEOL Ltd.), and the condition at the time of photographing was a backscattered electron image at an accelerating voltage of 25 kV. The photographing magnification was 5000 times.

As shown in FIG. 2A, BaTiO ₃
A plate-like or needle-like precipitate phase mixed inside the dielectric matrix phase containing as a main component was observed.

Comparative Example 9 Yb in the fourth subcomponent (oxide of R1) was 0 mol%,
4 mol% Y mol% in the fifth subcomponent (oxide of R2)
Example 1 except that the sintering temperature was 1325 ° C.
In the same manner as above, a prismatic ceramics sintered body sample was prepared.

An SEM photograph of the sample was taken in the same manner as in Example 16. The photograph is shown in FIG.

As shown in FIG. 2B, no plate-like or needle-like precipitation phase was observed.

Example 17 Yb in the fourth subcomponent (oxide of R1) was 4.3 mol% and the mol% of Y in the fifth subcomponent (oxide of R2) was 8.
A prismatic columnar ceramics sintered body sample was prepared in the same manner as in Example 1 except that the content was set to 00 mol% and the sintering temperature was set to 1325 ° C.

An SEM photograph of the sample was taken in the same manner as in Example 16. The photograph is shown in FIG.

As shown in FIG. 3A, BaTiO ₃
A plate-like or needle-like precipitate phase mixed inside the dielectric matrix phase containing as a main component was observed.

Comparative Example 10 Yb in the fourth subcomponent (oxide of R1) was set to 4.3 mol%, and mol% of Y in the fifth subcomponent (oxide of R2) was set to 0 mol%, followed by baking. A prismatic ceramics sintered body sample was prepared in the same manner as in Example 1 except that the binding temperature was 1280 ° C.

An SEM photograph of the sample was taken in the same manner as in Example 16. The photograph is shown in FIG.

As shown in FIG. 3B, no plate-like or needle-like precipitation phase was observed.

Example 18 Yb in the fourth subcomponent (oxide of R1) was 4.3 mol%, and mol% of Y in the fifth subcomponent (oxide of R2) was 4.
0 mol% and a sintering temperature of 1325 ° C.
In the same manner as in Example 1, a prismatic ceramics sintered body sample was prepared.

A secondary electron image on the surface of the sample was photographed with an electron microscope (product number C800 manufactured by Hitachi, Ltd.). A photograph with a magnification of 1000 times is shown in FIG. 4 (A), and a photograph with a magnification of 3000 times is shown in FIG. 4 (B).

As shown in FIGS. 4 (A) and 4 (B), plate-like or needle-like precipitation phases mixed in the dielectric matrix phase containing BaTiO ₃ as the main component were observed.

[0120]

As described above, according to the present invention, the relative dielectric constant is high and the capacitance-temperature characteristic is X8 of EIA standard.
A dielectric ceramic composition satisfying R characteristics (-55 to 150 ° C., ΔC = ± 15% or less), capable of firing in a reducing atmosphere, and excellent in mechanical strength, and this dielectric An electronic component such as a laminated ceramic capacitor using a porcelain composition can be provided.

[Brief description of drawings]

FIG. 1 is a sectional view of a monolithic ceramic capacitor according to an embodiment of the present invention.

FIG. 2 (A) is a SEM photograph (backscattered electron image) of a dielectric ceramic composition according to an example of the present invention, and FIG. 2 (B) is a dielectric ceramic composition according to a comparative example of the present invention. It is a SEM photograph (reflection electron image) of a thing.

FIG. 3 (A) is an SEM photograph (reflected electron image) of a dielectric ceramic composition according to another embodiment of the present invention, FIG. 3 (B).
Is an SEM of a dielectric ceramic composition according to another comparative example of the present invention.
It is a photograph (reflected electron image).

4A and 4B are SEM photographs (secondary electron images) of dielectric ceramic compositions according to other examples of the present invention.
Is.

[Explanation of symbols]

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

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shigeki Sato             1-13-1, Nihonbashi, Chuo-ku, Tokyo             -In DC Inc. F-term (reference) 4G031 AA03 AA04 AA05 AA06 AA07                       AA08 AA11 AA13 AA16 AA17                       AA18 AA19 AA30 BA09 CA01                       CA03 CA05                 5E001 AB03 AC09 AE00 AE01 AE02                       AE03 AE04                 5G303 AA01 AB11 AB12 BA12 CA01                       CB03 CB06 CB10 CB17 CB30                       CB32 CB35 CB36 CB37 CB40                       CB41 CB43

Claims (10)

[Claims] 1. BaTiO _{3 as a} main component and MgO, CaO, BaO, SrO and Cr ₂ O ₃
A first subcomponent containing at least one selected from (Ba, Ca) _x SiO _{2 + x} (where x = 0.
8 to 1.2), a second subcomponent represented by the formula (8 to 1.2), a third subcomponent containing at least one selected from V ₂ O ₅ , MoO ₃ and WO _3, and an oxide of R1 (wherein R1 is Yb) as a fourth subcomponent and an oxide of R2 (wherein R2 is Y, Dy, Ho, Tb,
A dielectric porcelain composition comprising at least a fifth subcomponent containing at least one selected from Gd and Eu), wherein the ratio of each subcomponent to 100 moles of BaTiO _{3 as} the main component is the first subcomponent. : 0.1-3 mol, 2nd subcomponent: 2-10 mol, 3rd subcomponent: 0.01-0.5 mol, 4th subcomponent: 0.5-7 mol (however, 4th subcomponent) Is the ratio of R1 alone), the fifth subcomponent: 2 to 9 mol (however, the mole number of the fifth subcomponent is the ratio of R2 alone), object. 2. A sixth subcomponent further contains MnO, and the content of the sixth subcomponent is BaTi as the main component.
The amount is 0.5 mol or less with respect to 100 mol of O _3.
The dielectric porcelain composition described in 1. 3. The total content of the fourth subcomponent and the fifth subcomponent is 13 mol or less per 100 mol of the main component BaTiO ₃ (however, the number of moles of the fourth subcomponent and the fifth subcomponent is Is a ratio of R1 and R2 alone), The dielectric ceramic composition according to claim 1 or 2. 4. A dielectric matrix phase containing BaTiO ₃ as a main component, and a plate-like or acicular precipitation phase mixed inside the dielectric matrix phase. The dielectric ceramic composition described. 5. An electronic component having a dielectric layer, wherein the dielectric layer comprises BaTiO _{3 as} a main component, MgO, CaO, BaO, SrO and Cr ₂ O ₃
A first subcomponent containing at least one selected from (Ba, Ca) _x SiO _{2 + x} (where x = 0.
8 to 1.2), a second subcomponent represented by the formula (8 to 1.2), a third subcomponent containing at least one selected from V ₂ O ₅ , MoO ₃ and WO _3, and an oxide of R1 (wherein R1 is Yb) as a fourth subcomponent and an oxide of R2 (wherein R2 is Y, Dy, Ho, Tb,
And a fifth subcomponent containing at least one selected from Gd and Eu), wherein the ratio of each subcomponent to 100 mol of BaTiO _{3 as} the main component is the first subcomponent. : 0.1-3 mol, 2nd subcomponent: 2-10 mol, 3rd subcomponent: 0.01-0.5 mol, 4th subcomponent: 0.5-7 mol (however, 4th subcomponent) Is the ratio of R1 alone), and the fifth subcomponent is 2 to 9 mol (however, the number of moles of the fifth subcomponent is the ratio of R2 alone). 6. The dielectric layer comprises M as a sixth subcomponent.
The electronic component according to claim 5, further comprising nO, wherein the content of the sixth subcomponent is 0.5 mol or less with respect to 100 mol of BaTiO _{3 as} a main component. 7. The total content of the fourth subcomponent and the fifth subcomponent is 13 mol or less with respect to 100 mol of the main component BaTiO ₃ (however, the number of moles of the fourth subcomponent and the fifth subcomponent is Is a ratio of R1 and R2 alone), The electronic component according to claim 5 or 6. 8. An electronic component having a dielectric layer, wherein the dielectric layer has a dielectric matrix phase containing BaTiO ₃ as a main component and a plate-like structure mixed inside the dielectric matrix phase, or The electronic component according to claim 5, which has a needle-shaped precipitation phase. 9. The capacitor element main body, wherein the dielectric layers and the internal electrode layers are alternately laminated together.
8. The electronic component according to any one of 8. 10. The conductive material contained in the internal electrode layer is N
The electronic component according to claim 9, which is an i or Ni alloy.