JP2005213126A - Reduction-resistant dielectric composition and ceramic electronic component using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reduction-resistant dielectric composition prepared by uniformly dispersing a sintering additive component into a main component without segregation and a ceramic electronic component using the reduction-resistant dielectric composition, having excellent reliable durability, small self-heating in high frequency current and excellent charcteristics for medium/high voltage. <P>SOLUTION: The reduction-resistant dielectric composition is obtained by successively carrying out a process for preparing a colloidal suspension containing the sintering additive component expressed by general formula, (Ca<SB>1-X</SB>Ba<SB>X</SB>)SiO<SB>3</SB>(where 0≤X≤1) by dropping ammonia water while stirring and mixing acetate aqueous solution of at least one or more kinds of Ca and Ba with a metal alkoxide ethanol solution of Si and a process for preparing raw material powder by mixing the colloidal suspension with powder of a main component expressed by general formula, (Sr<SB>1-X</SB>Ca<SB>X</SB>)<SB>m</SB>(Ti<SB>1-Y</SB>Zr<SB>Y</SB>)O<SB>2+m</SB>(where 0.55≤X≤0.85, 0.80≤Y≤1.00 and 993≤m≤1,007) and a trace quantity of an additive. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention provides a transistor snubber circuit for a switching power supply in which an internal electrode is made of a base metal, satisfies JIS standard COG characteristics, and a high-frequency current flows, so that a high Q value (reciprocal of dielectric loss coefficient) is required and low self-heating is required. Typical examples of multilayer ceramic capacitors widely used for medium- and high-voltage applications in inverter power supply circuits for backlights that make up liquid crystal display panels (LCDs) and anti-surge circuits for communication digital modems that require low distortion The present invention relates to a ceramic electronic component to be manufactured and a reduction-resistant dielectric composition for producing the same.

  In recent years, ceramic peripherals, which are one of the important passive components used for PC peripheral devices such as communication modems, LCDs, and switching power supplies, and electronic communication devices are becoming more and more compact. The transition of this technology is progressing rapidly, contributing to the miniaturization of switching power supply circuits and modem circuits, the resin molding, and the thinning of LCDs. In addition, according to the data of the credit bureau, it is certain that the lamination rate of ceramic capacitors will exceed 90% in the year 2005, and not only low rated voltage products but also medium and high voltage products, as well as safety standard products. It is a matter of time for the lamination to spread.

  For example, a transistor snubber circuit of a switching power supply in which a high-frequency current of about 100 KHz flows uses a medium-high voltage multilayer ceramic capacitor that satisfies a JIS standard SL characteristic with a rated voltage of 2 to 3 KVDC and a capacitance of several tens of pF. This contributes to miniaturization of the circuit. In addition, the LCD inverter power supply circuit is used for medium- and high-voltages that satisfy the JIS standard SL characteristics with a rated voltage of 3 KVDC and a capacitance of several tens to 100 pF, instead of the conventional disk type, as LCDs become thinner. Multilayer ceramic capacitors are being applied.

  The above-mentioned medium- and high-voltage multilayer ceramic capacitor has a structure in which a plurality of ceramic dielectric layers and internal electrode layers are alternately stacked to form an effective layer for obtaining capacitance, and the entire dimension adjustment and internal structure are formed above and below the effective layer. An ineffective layer consisting only of a ceramic dielectric layer is formed for hermetic sealing. The internal electrode layers are electrically connected by providing external electrodes on both end faces where the terminal portions are exposed, and Ni plating is performed on these external electrode surfaces so that they can be easily soldered and mounted. It has a structure in which Sn plating or Cu plating is applied in layers.

Conventionally, a multilayer ceramic capacitor for medium to high voltage satisfying JIS standard SL characteristics for such applications has been required to have low loss and not to generate abnormal heat due to high frequency current. In the SrTiO ₃ —CaTiO ₃ system, several types of additives are added, and the main component SrTiO ₃ —CaTiO ₃ —MgTiO ₃ system includes ZrO ₂ , Nb ₂ O ₅ , Ta ₂ O as additives. ₅ , a composition to which V ₂ O _{5 and the} like are added is disclosed. According to this, the rate of change in capacitance temperature is controlled by the ratio of the compounds constituting the main component, and the breakdown voltage and insulation are controlled by the additive. It is described that the resistance value is improved (see, for example, Patent Document 1).

  However, the dielectric composition does not have reduction resistance, and is premised on the use of a Pd-based noble metal as an internal electrode. There was a problem in terms. As a method for solving this problem, it is known to use low-cost Ni or an alloy containing Ni as a main component instead of Pd-based noble metals, and the proportion of base metal internal electrode products in the medium- and high-pressure multilayer ceramic capacitors is increased. There is a tendency.

Since Ni is a base metal, it cannot be fired in an oxygen atmosphere like conventional noble metal multilayer ceramic capacitors, and must be fired so that Ni is not oxidized in a low oxygen partial pressure atmosphere. A perovskite oxide expressed by the general formula of ABO ₃ which is well known for ceramic capacitors is reduced when exposed to an atmosphere below the Ni redox equilibrium oxygen partial pressure at a high temperature of 1,000 ° C. or higher, resulting in an insulation resistance value. Or the reliability test in a state where an electric field is applied, that is, a failure rate in a so-called load life increases, and the function as a dielectric for a capacitor is not achieved.

In response to this problem, these perovskite oxides can change the stoichiometric ratio of ions existing at the A site and B site, or can be dissolved in the lattice as a donor, such as transition metal ions. As a result, many reduction-resistant dielectric compositions composed of a perovskite oxide and a small amount of an additive have been devised, taking advantage of the property that it is difficult to reduce even if heat treatment as described above is performed, It is disclosed. The previous reduction-resistant dielectric composition has JIS standard F characteristics with a large capacitance temperature change rate, but JIS standard B characteristics or EIA standard X7R characteristics with a small capacitance temperature change rate are the mainstream. In recent years, however, active material development has been carried out, and low dielectric constant JIS standard COG characteristics or JIS standard SL characteristics, which have been difficult to be made into base metals, have been applied to multilayer ceramic capacitors. For example, Japanese Patent Application Laid-Open No. 2002-80278 contains V ₂ O ₅ and MnCO ₃ as additives and a SiO ₂ —CaO compound as a sintering aid with respect to the main component SrTiO ₃ —CaTiO ₃ . A reduction resistant dielectric composition is disclosed. As a result, large-capacity monolithic ceramic capacitors using a Ni-type internal electrode with a low distortion rate, excellent DC bias characteristics, and low cost are mainly commercialized mainly for low rated voltage products of 50 VDC.
Japanese Patent Laid-Open No. 7-211140

However, it is difficult to say that many of the conventional reduction-resistant dielectric compositions are designed in consideration of the uniform dispersibility and reactivity of trace additives with respect to the main component perovskite oxide. The characteristics and quality of the product fluctuate due to factors that cannot be controlled, causing a decrease in yield and poor reliability. For example, reduction-resistant dielectric composition prepared by calcination mixing method is a conventional process uniform sintering aid component, especially SiO ₂ -CaO-based and SiO ₂ -CaO-BaO based, etc. Among dopants It was difficult to disperse in the composition, and the sintering aid component was dispersed non-uniformly. As a result, a local abnormal reaction occurs in the reaction process during firing, resulting in a heterogeneous microstructure with large variations in crystal particle size and many pores, resulting in variations in capacitance and dielectric loss, and dielectric breakdown. The problem is that the voltage is low, the failure time distribution in the super accelerated life test (HALT) is wide, and the average failure time is short.

  Accordingly, the present invention provides a reduction-resistant dielectric composition in which the above-described problems are solved and the sintering aid component is uniformly dispersed in the main component without segregation, and the reduction-resistant dielectric is provided. Using the composition, ceramic electronic parts with high Q value, low self-heating under high-frequency current, excellent durability and reliability for medium and high pressure, and satisfying JIS standard COG characteristics with capacitance temperature change rate The purpose is to do.

In order to achieve this object, the reduction-resistant dielectric composition of the present invention is prepared by dropping ammonia water while stirring and mixing at least one acetate aqueous solution of Ca and Ba with a metal alkoxide ethanol solution of Si ( A step of preparing a colloidal suspension containing a component represented by the general formula of Ca _1-X Ba _X ) SiO ₃ (where 0 ≦ X ≦ 1), and the colloidal suspension (Sr _{1- X} Ca _X ) _m (Ti _1-Y Zr _Y ) O _{2 + m} (where 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) The raw material powder is manufactured by sequentially mixing with the main component powder and a small amount of additives. Thereby, uniform dispersion of the colloidal suspension containing Ca, Ba and Si is achieved, and the periphery of the main component SrTiO ₃ —CaZrO ₃ solid solution particles is uniformly coated with these components. A reduction-resistant dielectric composition capable of forming a very dense structure in which there is sometimes no local abnormal reaction and the sintering aid component is uniformly dispersed is obtained.

In addition, the amount of the component represented by the general formula of (Ca _1-X Ba _X ) SiO ₃ (where 0 ≦ X ≦ 1) contained in the colloidal suspension, and the types and amounts of the additives By defining for the main component powder, it is possible to realize ceramic electronic components represented by multilayer ceramic capacitors for medium to high pressure that have excellent initial characteristics and durability reliability, and have low self-heating under high-frequency current. A possible reduction-resistant dielectric composition is obtained.

  The ceramic electronic component of the present invention includes an effective layer in which an internal electrode layer made of Ni or an alloy containing Ni as a main component is provided between a plurality of first ceramic dielectric layers, and a second plurality of ceramic dielectric layers. A base having an ineffective layer, a pair of external electrodes provided from both ends to the side of the base and electrically joined to the internal electrode layer, and connected to the external electrode, respectively A molded ceramic electronic component in which the base body and the external electrode are embedded with resin, and the ceramic dielectric layer is made of the reduction-resistant dielectric composition, thereby providing a predetermined product standard value. Thus, a ceramic electronic component typified by a multilayer ceramic capacitor for medium and high voltage satisfying all of the above can be obtained.

As described above, according to the present invention, ammonia water is added dropwise (Ca _1-X Ba _X ) SiO ₃ while stirring and mixing at least one acetate aqueous solution of Ca and Ba and a metal alkoxide ethanol solution of Si. (However, a step of preparing a colloidal suspension containing a component represented by the general formula of 0 ≦ X ≦ 1), and the colloidal suspension (Sr _1−X Ca _X ) _m (Ti _{1− Y} Zr _Y ) O _{2 + m} (where 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) Colloidal suspension containing Ca, Ba, and Si because it is a reduction-resistant dielectric composition manufactured by sequentially performing a process of producing raw material powder by mixing with a small amount of additive for improvement (Sr _1-X Ca _X ) _m (Ti _1-Y Zr _Y ) O _{2 + m} (where 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) The solid solution particles are uniformly coated with these components. Therefore, there is no local abnormal reaction during firing, and a ceramic dielectric layer with a very dense structure in which the sintering aid components are uniformly dispersed is formed. It is possible to realize a Ni internal electrode multilayer ceramic capacitor having the characteristics.

Further, the amount of the sintering aid component represented by the general formula of (Ca _1−X Ba _X ) SiO ₃ (where 0 ≦ X ≦ 1), the kind of the additive, and the amount of the additive are specified. As a result, it is possible to realize a ceramic electronic component represented by a multilayer ceramic capacitor for high voltage in the Ni internal electrode, which has high product characteristics and excellent durability reliability in a circuit to which a high frequency pulse is applied.

  In addition, by using the reduction-resistant dielectric composition, chip-type, mold-type and lead-type Ni internal electrodes that can be used for medium-high voltage applications and can be designed in accordance with user requirements. A ceramic electronic component typified by a multilayer ceramic capacitor can be realized.

According to the first aspect of the present invention, ammonia water is added dropwise (Ca _1-X Ba _X ) while stirring and mixing at least one acetate aqueous solution of Ca and Ba and a metal alkoxide ethanol solution of Si. A step of preparing a colloidal suspension containing a component represented by the general formula of SiO ₃ (where 0 ≦ X ≦ 1), and the colloidal suspension is (Sr _1-X Ca _X ) _m (Ti _1-Y Zr _Y ) O _{2 + m} (where 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) And a reduction-resistant dielectric composition produced by sequentially performing a process of producing a raw material powder by mixing together with a small amount of additives, and having a good internal property and durability reliability for high pressure use A multilayer ceramic capacitor can be realized.

According to the second aspect of the present invention, ammonia water is dropped while stirring and mixing an aqueous solution of at least one acetate salt of Ca and Ba and a metal alkoxide ethanol solution of Si (Ca _1-X Ba _X ). A step of preparing a colloidal suspension containing a component represented by the general formula of SiO ₃ (where 0 ≦ X ≦ 1), and the colloidal suspension is (Sr _1-X Ca _X ) _m (Ti _1-Y Zr _Y ) O _{2 + m} (where 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) And a reduction-resistant dielectric composition manufactured by sequentially performing a process of preparing a raw material powder by mixing with a small amount of additives, and (Ca _1-X Ba _X ) SiO contained in the colloidal suspension ₃ (where, 0 ≦ X ≦ 1) component represented by the general formula, the (Sr _1-X C _{X) m (Ti 1-Y} Zr Y) O 2 + m ( where, represented by the general formula 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) A reduction-resistant dielectric composition characterized by being in the range of 1.0 to 5.0 moles with respect to 100 moles of the main component powder, and has good electrical properties and durability reliability for high pressure use It is possible to realize a Ni internal electrode multilayer ceramic capacitor having the characteristics.

In the invention according to claim 3 of the present invention, ammonia water is added dropwise (Ca _1-X Ba _X ) while stirring and mixing at least one of an aqueous solution of acetate of Ca and Ba and a metal alkoxide ethanol solution of Si. A step of preparing a colloidal suspension containing a component represented by the general formula of SiO ₃ (where 0 ≦ X ≦ 1), and the colloidal suspension is (Sr _1-X Ca _X ) _m (Ti _1-Y Zr _Y ) O _{2 + m} (where 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) In addition, in the reduction-resistant dielectric composition manufactured by sequentially performing a process of preparing a raw material powder by mixing with a small amount of additive, the additive is the (Sr _1-X Ca _X ) _m (Ti _{1 -Y Zr Y) O 2 + m} ( where, 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 99 ≦ respect m ≦ 1.007 powder 100 moles of the main component represented by the general formula), each Mn ₃ O ₄ is in the range of 0.05 to 2.0 mole, V ₂ O ₅ is 0.01 In the range of ~ 0.3 mol, Al203 in the range of 0.05 to 1.0 mol, CeO2 in the range of 0.01 to 2.0 mol, and MgO in the range of 0.01 to 0.2 mol. It is possible to realize a Ni internal electrode multilayer ceramic capacitor which is a reduction-resistant dielectric composition characterized in that it has good electrical characteristics and durability reliability for high voltage use.

In the invention according to claim 4 of the present invention, ammonia water is dropped while stirring and mixing at least one of an aqueous solution of acetate of Ca and Ba and a metal alkoxide ethanol solution of Si (Ca _1-X Ba _X ). A step of preparing a colloidal suspension containing a component represented by the general formula of SiO ₃ (where 0 ≦ X ≦ 1), and the colloidal suspension is (Sr _1-X Ca _X ) _m (Ti _1-Y Zr _Y ) O _{2 + m} (where 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) And a reduction-resistant dielectric composition manufactured by sequentially performing a process of preparing a raw material powder by mixing with a small amount of additives, and (Ca _1-X Ba _X ) SiO contained in the colloidal suspension ₃ (where, 0 ≦ X ≦ 1) component represented by the general formula, the (Sr _1-X C _{X) m (Ti 1-Y} Zr Y) O 2 + m ( where, represented by the general formula 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) The additive is contained in the range of 1.0 to 5.0 moles with respect to 100 moles of the main component powder. Further, the additive is the (Sr _1-X Ca _X ) _m (Ti _1-Y Zr _Y ) O _{2 + m} (however, 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) On the other hand, Mn ₃ O ₄ is in the range of 0.05 to 2.0 mol, V ₂ O ₅ is in the range of 0.01 to 0.3 mol, and Al ₂ O ₃ is 0.05 to 1.0. A reduction-resistant dielectric composition characterized by having a molar range, CeO ₂ within a range of 0.01 to 2.0 mol, and MgO within a range of 0.01 to 0.2 mol. For high pressure It is possible to realize the Ni internal electrode multilayer ceramic capacitor having excellent electric properties and durability and reliability.

  According to a fifth aspect of the present invention, an effective layer in which an internal electrode layer made of Ni or an alloy containing Ni as a main component is provided between the first plurality of ceramic dielectric layers and the second plurality of ceramics. A chip type comprising: a base having an ineffective layer made of a dielectric layer; and a pair of external electrodes provided from both ends of the base to the side and electrically joined to the internal electrode layer A ceramic electronic component, wherein the ceramic dielectric layer is composed of the reduction-resistant dielectric composition according to any one of claims 1 to 4, and has high product characteristics. In addition, it is possible to realize a ceramic electronic component typified by a multilayer ceramic capacitor for medium-high voltage Ni internal electrodes having excellent durability and reliability in a circuit to which a high-frequency pulse is applied.

  According to a sixth aspect of the present invention, there is provided an effective layer in which an internal electrode layer made of Ni or an alloy containing Ni as a main component is provided between the first plurality of ceramic dielectric layers, and the second plurality of ceramics. A base having an ineffective layer made of a dielectric layer, a pair of external electrodes provided from both ends of the base to the side, and electrically joined to the internal electrode layer; and A reduction-resistant dielectric composition according to any one of claims 1 to 4, wherein the ceramic dielectric layer is a molded ceramic electronic component including a connected terminal, and the base and the external electrode are embedded with a resin. A ceramic electronic component characterized in that it is composed of a product, and has high product characteristics and has excellent durability and reliability in a circuit to which a high-frequency pulse is applied. It is possible to realize a ceramic electronic component typified by a click capacitor.

  According to a seventh aspect of the present invention, there is provided an effective layer in which an internal electrode layer made of Ni or an alloy containing Ni as a main component is provided between the first plurality of ceramic dielectric layers, and the second plurality of ceramics. A base having an ineffective layer made of a dielectric layer, a pair of external electrodes provided from both ends of the base to the side, and electrically joined to the internal electrode layer; and A reduction-resistant dielectric according to any one of claims 1 to 4, wherein the ceramic dielectric layer is a lead-type ceramic electronic component comprising a connected lead wire, the base and the external electrode being covered with a resin. A ceramic electronic component comprising a composition, having high product characteristics, and having excellent durability and reliability in a circuit to which a high-frequency pulse is applied. It is possible to realize a ceramic electronic component typified by a click capacitor.

  According to an eighth aspect of the present invention, the external electrode has a two-layer structure of an upper layer and a lower layer, and the lower layer is provided only on an end surface of the base. A ceramic electronic component represented by a multilayer ceramic capacitor for high voltage in Ni internal electrode, having high product characteristics and excellent durability reliability in a circuit to which a high frequency pulse is applied. Can be realized.

  Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a cross-sectional view showing an embodiment of the ceramic electronic component of the present invention. According to this, the ceramic dielectric layer as an ineffective layer above and below the effective layer serving as a capacitance acquisition layer formed by alternately laminating the ceramic dielectric layer 13 and the internal electrode layers 12a, 12b, and 12c containing Ni. 13 is laminated to form a laminated body 11, and the internal electrode layer 1 is formed at both ends of the laminated body 11.
2b and 12c, a Ni-type lower external electrode 14 that is electrically joined to each other is provided, and an Ag-type upper external electrode 15 is provided thereon.

  FIG. 2 is a cross-sectional view showing an embodiment of the ceramic electronic component of the present invention. According to this, the ceramic dielectric layer as an ineffective layer above and below the effective layer serving as a capacitance acquisition layer formed by alternately laminating the ceramic dielectric layer 23 and the internal electrode layers 22a, 22b, and 22c containing Ni. 23 is laminated to form a laminated body 21, and Ni-type lower external electrodes 24 electrically connected to the internal electrode layers 22 b and 22 c are provided at both ends of the laminated body 21, and Ag quality is provided thereon. The upper layer external electrode 25 is provided. Then, conductive terminals 27 are drawn from both end portions of the laminate 21 embedded in the thermosetting resin 26, and are configured to be surface-mounted on the circuit board via the terminals 27.

  FIG. 3 is a cross-sectional view showing an embodiment of the ceramic electronic component of the present invention. According to this, the ceramic dielectric layer as an ineffective layer above and below the effective layer serving as a capacitance acquisition layer formed by alternately laminating the ceramic dielectric layer 33 and the internal electrode layers 32a, 32b, and 32c containing Ni. 33 is laminated to form a laminated body 31, and Ni-based lower external electrodes 34 electrically connected to the internal electrode layers 32b and 32c are provided at both ends of the laminated body 31, and Ag is formed thereon. In this configuration, a high-quality external electrode 35 is provided. Then, conductive lead wires 37 are drawn out from both end portions of the laminate 31 covered with the exterior material 36, and can be soldered to the circuit board via the lead wires 37. The medium and high voltage multilayer ceramic capacitors having the three types of structures can be selectively used according to the user's request by taking advantage of their respective characteristics. Particularly, the mold type and the lead type medium and high voltage multilayer ceramic capacitors are abnormal. There is no worry of creeping discharge due to voltage, and the terminals and lead wires drawn from both ends of each laminate are soldered to the circuit board, so even if the circuit board is bent, the laminate body has Since no mechanical stress is applied, the circuit design is extremely superior.

And, the reduction-resistant dielectric composition constituting the ceramic dielectric layer of the above-mentioned medium-high voltage multilayer ceramic capacitor is prepared by stirring and mixing at least one acetate aqueous solution of Ca and Ba with a metal alkoxide ethanol solution of Si. A colloidal suspension containing a component represented by the general formula of (Ca _1-X Ba _X ) SiO ₃ (where 0 ≦ X ≦ 1) by dropping ammonia water while (Sr _1−X Ca _X ) _m (Ti _1−Y Zr _Y ) O _{2 + m} (where 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) is produced by sequentially carrying out a raw material powder by mixing with the main component powder represented by the general formula and a trace amount of additives, preferably the colloidal suspension contained in the liquid _{(Ca 1-X Ba X)} SiO 3 However, components of the general formula of 0 ≦ X ≦ 1), the _{(Sr 1-X Ca X)} m (Ti 1-Y Zr Y) O 2 + m ( where 0.55 ≦ X ≦ 0 .850 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) with respect to 100 moles of the main component powder represented by the general formula: 1.0 to 5.0 moles, and the additive Is (Sr _1−X Ca _X ) _m (Ti _1−Y Zr _Y ) O _{2 + m} (where 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1. 007) with respect to 100 mol of the main component powder represented by the general formula: Mn ₃ O ₄ is in the range of 0.05 to 2.0 mol, and V ₂ O ₅ is 0.01 to 0.3 mol. In the range, Al203 is in the range of 0.05 to 1.0 mol, CeO2 is in the range of 0.01 to 2.0 mol, and MgO is in the range of 0.01 to 0.2 mol.

(Sr _1-X Ca _X ) _m (Ti _1-Y Zr _Y ) O _{2 + m} used in the practice of the present invention (provided that 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993) The powder of the main component represented by the general formula of ≦ m ≦ 1.007) preferably has a small average particle size and a narrow particle size distribution. In addition, it is preferable to use a powder having a high degree of crystallinity because the smaller the reactivity, the easier the expression of COG characteristics. Impurities mixed in the process of producing such a main component powder include alkaline earth metals other than strontium and calcium, iron, silicon and aluminum. These impurities are contained in the order of several thousand ppm. There is no particular problem. This (Sr _1−X Ca _X ) _m (Ti _1−Y Zr _Y ) O _{2 + m} (where 0.55 ≦ X ≦ 0.85
The powder of the main component represented by the general formula of 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) is a JIS standard COG characteristic (capacitance change rate within a temperature range of −55 to + 125 ° C.). 0 ± 30 ppm / ° C.) is the most important. This compound is synthesized from each powder of SrTiO ₃ —CaZrO ₃ or each powder of SrCO ₃ —CaCO ₃ —TiO ₂ —ZrO ₂ by solid phase reaction. Specifically, in order to produce a multilayer ceramic capacitor for medium to high pressure, which is a ceramic electronic component of the present invention, synthesized at a calcination temperature of 1100 to 1300 ° C. and passing through a pulverization process or the like, 4.0 to 7.0 m Adjusted to a powder with a BET value of ² / g.

  Ca and Ba acetates and Si alkoxides, which are starting materials for colloidal suspensions mixed with powders of main components, can be used as commercially available products, and impurities contained therein are metals having similar chemical properties. Therefore, even if it is contained in the order of several thousand ppm like the above-mentioned main component, there is no particular problem. Moreover, a general commercial item can also be used for ethanol in which the alkoxide is dissolved.

  These acetates and alkoxides exist as hydrated ions in a water-ethanol solution, and fine hydroxide is produced in the form of a colloidal suspension by the subsequent dropwise addition of aqueous ammonia, which is then used as the main powder. When mixed with, it is desirable that the aqueous ammonia be dispersed in a uniform state. Therefore, the concentration of ammonia water is 1 mol / liter or less, and it is desirable to lower the concentration when there is a sufficient facility and time for the process. When the concentration of ammonia water exceeds 1 mol / liter, the above-mentioned hydroxide is generated unevenly and mixed with the main component powder in a compositionally non-uniform state. The result is a uniform reduction resistant dielectric composition, which is completely different from what is intended by the present invention.

In the main component (Sr _1−X Ca _X ) _m (Ti _1−Y Zr _Y ) O _{2 + m} , x is in the range of 0.55 ≦ X ≦ 0.85. When X is less than 0.55, it deviates from the JIS standard COG characteristics, and when X exceeds 0.85, the dielectric constant is remarkably lowered. Y is in the range of 0.80 ≦ Y ≦ 1.00. When Y is less than 0.80, the Q value decreases and self-heating increases. Furthermore, m is in the range of 0.993 ≦ m ≦ 1.007. If m is less than 0.993, grain growth is promoted in the ceramic dielectric layer, and at the same time the reduction resistance is impaired, so that the Q value is lowered and the dielectric breakdown voltage is degraded. On the other hand, if m exceeds 1.007, the ceramic dielectric layer is difficult to sinter and has a high sintering temperature to obtain a dense sintered body.

(Sr _1-X Ca _X ) _m (Ti _1-Y Zr _Y ) O _{2 + m} (however, 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) The amount of each additive added to 100 moles of the main component powder represented by the general formula is a dielectric constant, a Q value, and a temperature change rate of capacitance, which are product characteristics of the multilayer ceramic capacitor for medium to high pressure In terms of insulation resistance, dielectric breakdown voltage, high temperature load life, self-heating, and reduction resistance at the firing temperature.

(Sr _1-X Ca _X ) _m (Ti _1-Y Zr _Y ) O _{2 + m} (however, 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) When Mn ₃ O ₄ exceeds 2.0 mol with respect to 100 mol of the main component powder represented by the general formula, the temperature change rate of the capacitance increases, deviating from the JIS standard COG characteristics, and 0. When it is less than 05 mol, the reduction resistance is impaired, the Q value is lowered, and the insulation resistance and the breakdown voltage are deteriorated. When V ₂ O ₅ exceeds 0.3 mol with respect to 100 mol of the main component powder, the reduction resistance is impaired and easily reduced, and the insulation resistance and breakdown voltage are deteriorated. High temperature load life is shortened. When Al ₂ O ₃ exceeds 1.0 mol with respect to 100 mol of the main component powder, it becomes difficult to sinter and the dielectric constant decreases, and when it is less than 0.05 mol, the high temperature load life is shortened. When CeO2 exceeds 2.0 moles with respect to 100 moles of the main component powder, the insulation resistance and breakdown voltage deteriorate, and when it is less than 0.01 moles, the high temperature load life is shortened. When MgO exceeds 0.2 mol with respect to 100 mol of the main component powder, the Q value decreases and self-heating increases, and when it is less than 0.01 mol, the high temperature load life is shortened.

Further, (Sr _1−X Ca _X ) _m (Ti _1−Y Zr _Y ) O _{2 + m} (however, 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1. 007) with respect to 100 moles of the main component powder represented by the general formula (Ca _1-X Ba _x ) SiO ₃ (where 0 ≦ X ≦ 1) If it exceeds 5.0 mol, the dielectric constant decreases and the high-temperature load life deteriorates, and if it is less than 1.0 mol, the effect as a sintering aid component cannot be obtained and densification by firing becomes incomplete, and at the same time Q The value decreases and self-heating increases.

  Next, a detailed manufacturing method of the multilayer ceramic capacitor for medium and high voltage which is one of the ceramic electronic components of the present invention will be described.

(Sr _1−X Ca _X ) _m (Ti _1−Y Zr _Y ) O _{2 + m} (where 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦) A predetermined amount of each of Mn ₃ O ₄ , V ₂ O ₅ , Al ₂ O ₃ , CeO ₂ , and MgO, which are powders represented by the general formula (1.007) and additives, is added to the electronic balance based on the composition table. Weigh and put into a polyethylene pot mill with an internal volume of 600 CC containing 350 g of 5 mmφ ZrO ₂ quality balls. Next, after predetermined amounts of Ba, Ca acetate and TEOS (tetraethoxysilane) were weighed with an electronic balance based on the same composition table, acetate was separated into 100 CC pure water, and TEOS was separated into 150 CC ethanol. Dissolve in. Then, an aqueous acetate solution was put into the ethanol solution, and a predetermined amount of 1N ammonia water was dropped while continuing to stir with a propeller stirrer, and (Ca _1-X Ba _X ) SiO ₃ (where 0 ≦ X ≦ A colloidal suspension containing a sintering aid component represented by the general formula 1) was obtained.

  Next, the colloidal suspension was put into the pot mill and mixed for 20 hours at a rotation speed of 100 rpm. The mixture was filtered through a 150 mesh silk screen, placed in a stainless steel vat lined with a Teflon sheet, and dried at a temperature of 120 ° C. using an explosion proof dryer. The dried lump was crushed in an alumina mortar, passed through a 32 mesh nylon sieve, placed in an alumina crucible, and heat treated under conditions of 400 ° C./2 hours to obtain a slurry powder.

  Next, the slurry powder was wetted by mixing with a predetermined amount of solvent and plasticizer. After wetting, a vehicle made of polyvinyl butyral resin was mixed to prepare a sheet forming slurry.

  Next, the slurry was filtered through a 150 mesh silk screen, and then formed into a film to obtain a ceramic raw sheet. Then, the ceramic raw sheet and an internal electrode sheet made of Ni paste were used for lamination based on a predetermined lamination specification by a transfer method, and then cut to obtain a green chip.

Next, after chamfering the obtained green chip, Ni paste used as a lower layer external electrode was applied to both end faces, dried, and then degreased. And reduction atmosphere baking was implemented with the rotary atmosphere furnace. Firing was held at a temperature of 1250 ° C. for 2 hours in an oxygen partial pressure atmosphere that was about two orders of magnitude lower than the equilibrium oxygen partial pressure of Ni adjusted with green gas, CO ₂ and N ₂ . Then, an Ag paste serving as an upper external electrode is applied to both end faces of the fired chip and baked in the air, and then Ni plating and Sn plating thereon are applied (FIG. 1). It is possible to obtain a chip-type medium / high voltage multilayer ceramic capacitor which is one of the ceramic electronic components of the invention.

  Also, after soldering conductive metal terminals to both end faces of the chip-type medium- and high-voltage multilayer ceramic capacitor element, the main parts of the element and metal terminals are embedded with a thermosetting resin (FIG. 2). As shown, it is possible to obtain a mold type medium and high voltage multilayer ceramic capacitor which is one of the ceramic electronic components of the present invention.

  Further, after soldering conductive lead wires to both end faces of the chip-type medium- and high-voltage multilayer ceramic capacitor element, the main part of the element and the lead wires are covered with an exterior material as shown in FIG. In addition, a lead-type medium / high voltage multilayer ceramic capacitor, which is one of the ceramic electronic components of the present invention, can be obtained.

  One of the ceramic electronic components obtained in this way is a multilayer ceramic capacitor for medium and high voltage, which has a ceramic dielectric layer made of a limited reduction-resistant dielectric composition, and has a fine structure. Because it has a very uniform and dense structure, the Q value is very high, the rate of change in capacitance temperature satisfies the JIS standard COG characteristics, self-heating is small under high-frequency current, and it is durable for medium- and high-pressure applications. It is excellent in reliability and is applied mainly to a circuit to which a high frequency high pulse is applied, such as an inverter power supply circuit of a backlight constituting an LCD. Further, the multilayer ceramic capacitor for medium and high voltage of the present invention can be used properly according to the user's request by taking advantage of the structural features of the chip type, mold type and lead type.

  Next, specific examples of the present invention will be described.

(Example 1)
The experimental procedure is (Sr _{1 -X} Ca _X ) _m (Ti _{1 -Y} Zr _Y ) O _{2 + m} (where 0.55 ≦ X ≦ 0) according to the composition table shown in (Table 1). .85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) and powders (manufactured by Kyoritsu Materials Co., Ltd.) and additives Mn ₃ O ₄ , V ₂ O ₅ , Al ₂ O ₃ , a mixture obtained by weighing a predetermined amount of each of CeO ₂ and MgO with an electronic balance and a colloidal suspension containing a sintering aid component composed of Ba, Ca and Si by a pot mill, Make a powder. The composition of the sintering aid component in Example 1 is (Ba _0.6 Ca _0.4 ) SiO ₃ .

  Next, using the produced powder, a Ni internal electrode chip type multilayer ceramic capacitor having a 3216 size shape as shown in FIG. 1 as a test sample is produced and comprehensively evaluated.

  The manufacturing method of the Ni internal electrode chip type multilayer ceramic capacitor as the test sample is the same as the series of procedures shown in the above embodiment.

  The evaluation items and evaluation method of the prototype Ni internal electrode chip type multilayer ceramic capacitor will be described below.

Capacitance (Cap) and Q value were measured using a YHP LCR meter 4284A under a signal voltage of 1 V / 1 MHz. The dielectric constant was calculated from the measured capacitance (Cap) value, the thickness of the ceramic dielectric layer of the prototype Ni internal electrode chip type multilayer ceramic capacitor, and the counter electrode area. The insulation resistance value (IR) was measured by applying 500 VDC for 1 minute using an insulation resistance meter R8340A manufactured by Advantest Corporation. With respect to the dielectric breakdown voltage (BDV), a DC breakdown voltage was measured in silicone oil using a pressure gauge made by Kikusui Electronics. The rate of change in capacitance temperature (Cap-TC) was measured within the range of 0 to + 125 ° C. by connecting a YHP LCR meter 4284A to a thermostat. Self-heating was measured at a voltage of 2 KV by gradually increasing the voltage while resonating at a frequency of 200 KHz by applying a resonance circuit using a coil inductance L and a capacitance Cap of the capacitor using a high frequency power source. As part of the reliability evaluation, a high temperature load test was performed by applying a voltage of 2.0 KVDC at a temperature of 125 ° C.

  The capacitance and Q value were each measured for 20 pieces, the insulation resistance value and the dielectric breakdown voltage were each 10 pieces, the temperature change rate of the capacitance and the self-heating two pieces were measured, and the average value was calculated. The high-temperature load test was performed by soldering and mounting 20 test samples, each prototyped with each composition, on a dedicated substrate, and then destroying 3 or more samples by 1000 hours. NG.

  These series of measurement results are shown in Table 2.

  Here, in Run No. of (Table 2). (Run No. in Table 1). It corresponds to. In addition, Run No. in (Table 2). Those marked with * are test samples in which good results were not obtained for at least one of the evaluation items, and are reduction-resistant dielectric compositions outside the scope of the present invention.

(Table 1) and (Table 2) As is clear from the main component in _{(Sr 1-X Ca X)} m (Ti 1-Y Zr Y) O 2 + m, the molar ratio X is less than 0.55 In this case, the rate of change in capacitance at + 125 ° C. increases, deviates from the JIS standard COG characteristics, and the insulation resistance value and Q value tend to decrease, and when the molar ratio X exceeds 0.85, the dielectric constant increases rapidly. Declined. When the molar ratio Y was less than 0.80, self-heating increased as the Q value decreased. Further, when the molar ratio m is less than 0.993, grain growth is remarkable in the ceramic dielectric layer, and at the same time, the reduction resistance is impaired. Therefore, the Q value is lowered and the dielectric breakdown voltage is further deteriorated. When m exceeded 1.007, the ceramic dielectric layer became difficult to sinter, a dense ceramic dielectric layer was hardly formed, and the dielectric constant was lowered.

100 mol of the main component powder represented by (Sr _1-X Ca _X ) _m (Ti _1-Y Zr _Y ) O _{2 + m} (where X = 0.698 Y = 0.972 m = 0.998) On the other hand, when Mn ₃ O ₄ exceeds 2.0 mol, the rate of change in capacitance temperature increases, and when it is less than 0.05 mol, the reduction resistance is impaired, the Q value decreases, the insulation resistance and Dielectric breakdown voltage deteriorated, self-heating increased, and high temperature load life deteriorated. When AL ₂ O ₃ exceeds 1.0 mol with respect to 100 mol of the main component powder, the dielectric constant decreases rapidly, and the Q value and the insulation resistance tend to deteriorate. A failure occurred in the load life test. When CeO ₂ exceeds 2.0 mol with respect to 100 mol of the main component powder, the insulation resistance and dielectric breakdown voltage are lowered, and when it is less than 0.01 mol, problems occur in the high temperature load life test. When MgO exceeds 0.2 mol with respect to 100 mol of the main component powder, the Q value decreases and self-heating increases, and when it is less than 0.01 mol, the high temperature load life is shortened. When V ₂ O ₅ exceeds 0.3 mol with respect to 100 mol of the main component powder, the reduction resistance is impaired and easily reduced, the insulation resistance and the breakdown voltage are deteriorated, and less than 0.01 mol If it becomes, the high temperature load life will become short.

Further, (Sr _1−X Ca _X ) _m (Ti _1−Y Zr _Y ) O _{2 + m} (where X = 0.698 Y = 0.972 m = 0.998) When the sintering aid component represented by the general formula of (Ca _0.4 Ba _0.6 ) SiO ₃ exceeds 5.0 moles with respect to 100 moles of the component powder, the dielectric constant decreases and the high temperature load life deteriorates. When the amount was less than 1.0 mol, the effect as a sintering aid component was not obtained, and densification by firing became incomplete, and at the same time, the Q value was lowered and self-heating was increased.

  On the other hand, the Ni internal electrode chip type multilayer ceramic capacitor produced by the reduction-resistant dielectric composition within the scope of the present invention has good sinterability and reduction resistance, and the capacitance changes with temperature. The rate satisfied the JIS standard COG characteristics, and at the same time had electrical characteristics suitable for medium- and high-pressure applications, small self-heating under high-frequency current, and excellent durability and reliability.

  As described above, according to the reduction-resistant dielectric composition of the present invention, the high Q value and low heat generation optimum for a circuit to which a high frequency high pulse is applied, such as an inverter power supply of a backlight constituting an LCD. It is possible to realize a ceramic electronic component typified by a medium-high voltage chip type multilayer ceramic capacitor.

(Example 2)
Run No. in Table 1 (Sr _1−X Ca _X ) _m (Ti _1−Y Zr _Y ) O _{2 + m} (where X = 0.698 Y = 0.972 m = 0.998) A powder of a general formula (made by Kyoritsu Material) and a composition in which a predetermined amount of each of Mn ₃ O ₄ , V ₂ O ₅ , Al ₂ O ₃ , CeO ₂ and MgO as additives is weighed with an electronic balance; Colloidal suspensions containing sintering aid components consisting of Ba, Ca and Si are mixed in a pot mill to prepare each starting material powder. The composition of the sintering aid component in Example 2 is (Ba _0.6 Ca _0.4 ) SiO ₃ .

  Next, using the prepared powder, a chip-type medium / high pressure multilayer ceramic capacitor element was manufactured according to the procedure described in the above embodiment.

  Next, after soldering metal terminals to both end faces of the chip-type medium / high voltage multilayer ceramic capacitor element, the main part of the element and the metal terminal are embedded with an epoxy-based thermosetting resin (FIG. 2). As shown in the above, a mold type medium-high voltage multilayer ceramic capacitor, which is one of the ceramic electronic components of the present invention, was produced.

The produced mold type multilayer ceramic capacitor of Example 2 has (Sr _0.302 Ca _0.698 ) _0.998 (Ti _0.028 Zr _0.972 ) O _2.998 quality ceramic dielectric layer 23 and an internal electrode containing Ni as shown in FIG. (Sr _0.302 Ca _0.698 ) _0.998 (Ti _0.028 Zr _0.972 ) O _2.998 quality ceramic dielectric as an ineffective layer above and below the effective layer to be a capacitance acquisition layer formed by alternately laminating layers 22a, 22b and 22c A layered body 21 is formed by laminating the layers 23, and Ni-based lower layer external electrodes 24 electrically connected to the internal electrode layers 22b and 22c are provided at both ends of the layered body 21, on which the layered body 21 is formed. An Ag quality upper layer external electrode 25 was provided. Then, conductive metal terminals 27 are drawn out from both end portions of the laminate 21 embedded in the thermosetting resin 26 and can be surface-mounted on the circuit board via the metal terminals 27.

  Next, the bending strength of the mold type multilayer ceramic capacitor of Example 2 was measured. Deflection strength is an important evaluation item for judging the reliability of electronic components for surface mounting. After soldering the product under test to a dedicated printed circuit board, it is statically added with a 3-point bend using a dedicated jig. The capacitance is measured, and the deflection width (mm) of the substrate at the time when the capacitance value suddenly decreases is defined as the deflection strength. Usually, there are many cases in which a crack is generated in a product under test at the time when the capacitance value suddenly decreases. In the case of the mold type multilayer ceramic capacitor of Example 2, the capacitance value did not decrease and was stable even when the deflection width exceeded 15 mm. At the same time, in the case of the chip-type multilayer ceramic capacitor of Example 1, there was a product to be tested in which the deflection width (mm) was 6 mm and the capacitance value suddenly decreased and cracks occurred. Since the minimum value of the flexure strength standard is 2.0 mm, both are at a level where there is no problem, but the mold type was clearly superior.

  Further, the chip-type multilayer ceramic capacitor of Example 1 may cause creeping leakage due to condensation on the surface of the multilayer body with respect to abnormal voltage outside the standard, but the mold-type multilayer ceramic of Example 2 The capacitor has no possibility and has high durability and reliability.

  As described above, the mold-type multilayer ceramic capacitor of the present invention has a structure in which the main parts of the element and the metal terminal are embedded with an epoxy-based thermosetting resin, and thus has high reliability and excellent for medium and high pressure applications. It can achieve surface mountability and is ideal for inverter power supply circuits for backlights that make up liquid crystal display panels (LCDs) and surge circuits for communication digital modems that require low distortion. is there.

The reduction-resistant dielectric composition of the present invention is prepared by dropping ammonia water while stirring and mixing at least one acetate aqueous solution of Ca and Ba and a metal alkoxide ethanol solution of Si (Ca _1-X Ba _X ). A step of preparing a colloidal suspension containing a component represented by the general formula of SiO ₃ (where 0 ≦ X ≦ 1), and the colloidal suspension is (Sr _1-X Ca _X ) _m (Ti _1-Y Zr _Y ) O _{2 + m} (where 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) And a step of producing a raw material powder by mixing together with a small amount of additives. Thereby, uniform dispersion of the colloidal suspension containing Ca, Ba and Si is achieved, and the periphery of the main component SrTiO ₃ —CaZrO ₃ solid solution particles is uniformly coated with these components. A reduction-resistant dielectric composition capable of forming a very dense structure in which the sintering aid component is uniformly dispersed sometimes without any local abnormal reaction. A ceramic dielectric layer having a very dense structure in which the binder component is uniformly dispersed is formed, thereby realizing a Ni internal electrode multilayer ceramic capacitor having good electrical characteristics and durability reliability for medium and high pressure. It can also be applied to applications where this is necessary.

Sectional drawing which shows one Example of the ceramic electronic component of this invention Sectional drawing which shows one Example of the ceramic electronic component of this invention Sectional drawing which shows one Example of the ceramic electronic component of this invention

Explanation of symbols

11, 21, 31 Laminate 12a, 12b, 12c, 22a, 22b, 22c, 32a, 32b, 32c Internal electrode layer 13, 23, 33 Ceramic dielectric layer 14, 24, 34 Ni-based lower external electrode 15, 25, 35 Ag upper external electrode 26 Thermosetting resin 27 Terminal 36 Exterior material 37 Lead wire 38 Solder

Claims (8)

While stirring and mixing at least one of an aqueous acetate solution of Ca and Ba and a metal alkoxide ethanol solution of Si, ammonia water is added dropwise (Ca _1-X Ba _X ) SiO ₃ (where 0 ≦ X ≦ 1). a step of preparing a colloidal suspension containing a component represented by the general formula, the colloidal suspension _{(Sr 1-X Ca X)} m (Ti 1-Y Zr Y) O 2 + m ( where 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) and mixed with the main component powder represented by the general formula and a small amount of additives A reduction-resistant dielectric composition characterized by being manufactured by sequentially performing the manufacturing process. While stirring and mixing at least one of an aqueous acetate solution of Ca and Ba and a metal alkoxide ethanol solution of Si, ammonia water is added dropwise (Ca _1-X Ba _X ) SiO ₃ (where 0 ≦ X ≦ 1). a step of preparing a colloidal suspension containing a component represented by the general formula, the colloidal suspension _{(Sr 1-X Ca X)} m (Ti 1-Y Zr Y) O 2 + m ( where 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) and mixed with the main component powder represented by the general formula and a small amount of additives In the reduction-resistant dielectric composition manufactured by sequentially performing the manufacturing steps, (Ca _1-X Ba _X ) SiO ₃ (where 0 ≦ X ≦ 1) contained in the colloidal suspension ingredient of the formula, the _{(Sr 1-X Ca X)} m (Ti 1-Y Zr Y) O 2 + m ( 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) with respect to 100 moles of the main component powder represented by the general formula A reduction-resistant dielectric composition characterized by being in the range of 0.0 mol. While stirring and mixing at least one of an aqueous acetate solution of Ca and Ba and a metal alkoxide ethanol solution of Si, ammonia water is added dropwise (Ca _1-X Ba _X ) SiO ₃ (where 0 ≦ X ≦ 1). a step of preparing a colloidal suspension containing a component represented by the general formula, the colloidal suspension _{(Sr 1-X Ca X)} m (Ti 1-Y Zr Y) O 2 + m ( where 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) and mixed with the main component powder represented by the general formula and a small amount of additives In the reduction-resistant dielectric composition manufactured by sequentially performing the manufacturing process, the additive is the (Sr _1-X Ca _X ) _m (Ti _1-Y Zr _Y ) O _{2 + m} (where 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) Against powder 100 moles of the main component that, each Mn ₃ O ₄ is in the range of 0.05 to 2.0 mole, V ₂ O ₅ in the range of 0.01 to 0.3 mol, Al ₂ 0 ₃ In a range of 0.05 to 1.0 mol, CeO _{2 in} a range of 0.01 to 2.0 mol, and MgO in a range of 0.01 to 0.2 mol. A reducing dielectric composition. While stirring and mixing at least one of an aqueous acetate solution of Ca and Ba and a metal alkoxide ethanol solution of Si, ammonia water is added dropwise (Ca _1-X Ba _X ) SiO ₃ (where 0 ≦ X ≦ 1). a step of preparing a colloidal suspension containing a component represented by the general formula, the colloidal suspension _{(Sr 1-X Ca X)} m (Ti 1-Y Zr Y) O 2 + m ( where 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) and mixed with the main component powder represented by the general formula and a small amount of additives In the reduction-resistant dielectric composition manufactured by sequentially performing the manufacturing steps, (Ca _1-X Ba _X ) SiO ₃ (where 0 ≦ X ≦ 1) contained in the colloidal suspension ingredient of the formula, the _{(Sr 1-X Ca X)} m (Ti 1-Y Zr Y) O 2 + m ( 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) with respect to 100 moles of the main component powder represented by the general formula In the range of 0.0 mol, the additive may be (Sr _1−X Ca _X ) _m (Ti _1−Y Zr _Y ) O _{2 + m} (provided that 0.55 ≦ X ≦ 0.85 0.80 ≦ Y ≦ 1.00 993 ≦ m ≦ 1.007) with respect to 100 moles of the main component powder represented by the general formula, 0.05 to 2.0 Mn ₃ O ₄ respectively. the range of mole, in the range V ₂ O ₅ is 0.01 to 0.3 mol, Al203 in the range of 0.05 to 1.0 mol, the range CeO2 is 0.01 to 2.0 mole, And Mg
A reduction-resistant dielectric composition, wherein O is in the range of 0.01 to 0.2 mol. A base having an effective layer in which an internal electrode layer made of Ni or an alloy containing Ni as a main component is provided between the first plurality of ceramic dielectric layers, and an ineffective layer made of the second plurality of ceramic dielectric layers; A chip-type ceramic electronic component provided with a pair of external electrodes provided so as to extend from both ends to the side of the base body and electrically connected to the internal electrode layer, the ceramic dielectric layer being A ceramic electronic component comprising the reduction-resistant dielectric composition according to any one of claims 1 to 4. A base having an effective layer in which an internal electrode layer made of Ni or an alloy containing Ni as a main component is provided between the first plurality of ceramic dielectric layers, and an ineffective layer made of the second plurality of ceramic dielectric layers; A pair of external electrodes provided so as to extend from both ends of the base to the side and electrically joined to the internal electrode layer, and terminals connected to the external electrodes, respectively, 5. A ceramic electronic component having an electrode embedded with a resin, wherein the ceramic dielectric layer is composed of the reduction-resistant dielectric composition according to any one of claims 1 to 4. . A base having an effective layer in which an internal electrode layer made of Ni or an alloy containing Ni as a main component is provided between the first plurality of ceramic dielectric layers, and an ineffective layer made of the second plurality of ceramic dielectric layers; A pair of external electrodes provided so as to extend from both ends of the base to the side and electrically joined to the internal electrode layer, and lead wires respectively connected to the external electrodes, A lead-type ceramic electronic component in which an external electrode is coated with a resin, and the ceramic dielectric layer is composed of the reduction-resistant dielectric composition according to any one of claims 1 to 4. parts. 8. The ceramic electronic component according to claim 5, wherein the external electrode has a two-layer structure of an upper layer and a lower layer, and the lower layer is provided only on an end surface of the base.

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