CN1790568B - Dielectric ceramic composition, electronic device, and method for producing the same - Google Patents

Abstract

_A method _for producing _a dielectric ceramic _{composition ,} which comprises dielectric oxide, _manganese oxide, _oxide The dielectric ceramic composition of aluminum and sintering aids, the symbols x, y, z, m representing the composition molar ratio in the above structural formula are 0.5≤x≤1.0, 0.01≤y≤0.10, 0<z≤0.20, 0.90≤m ≤1.04, characterized in that the dielectric ceramic composition is manufactured using a sintering aid having: _SiO2 as the main component, and also containing MO (wherein, M is at least one of Ba, Ca, Sr and Mg ), a first glass composition; a second glass composition comprising B2O3, Al2O3, ZnO and SiO ₂ , having an average particle diameter of 1.5 μm or less. According to this invention, it is possible to provide a method for producing a dielectric ceramic composition capable of obtaining a dense dielectric ceramic composition without impairing various electrical properties even when fired at a low temperature.

Description

Dielectric ceramic composition, electronic component and their manufacturing method

technical field

The present invention relates to, for example, a dielectric ceramic composition used as a dielectric layer of a laminated ceramic capacitor and a method for producing the same, and an electronic component using the dielectric ceramic composition as a dielectric layer and a method for producing the same.

Background technique

An example of an electronic component, the structure of the dielectric ceramic composition of the dielectric layer of a laminated ceramic capacitor includes ferroelectric BaTiO ₃ , permanent dielectric SrTiO ₃ , CaTiO ₃ , CaSrZrO ₃ , CaZrO ₃ , SrZrO ₃ , TiO ₂ , NdTiO _{3 ,} etc. a dielectric oxide.

In recent years, reduction-resistant dielectric ceramic compositions have been developed. With this reduction-resistant dielectric ceramic composition, base metals such as Ni and Cu can be used as materials for internal electrodes without semiconductorization even when sintered in a neutral to reducing atmosphere with low oxygen partial pressure.

As such a dielectric ceramic composition, a CaSr-ZrTi-Mn-based material is known (refer to Patent Document 1). Usually, in addition to a dielectric oxide as a main component, a sintering aid for promoting sintering is added. In addition, calcination is performed at a high temperature of, for example, 1300° C. or higher.

However, when the sintering temperature is high, the following inconveniences arise.

First, the temperature range above or close to the melting point of the base metals such as Ni as the material for forming the internal electrodes, as a result, becomes a major cause of the following inconvenience: the base metal particles sintered simultaneously with the dielectric ceramic composition are fused and balled. , and the linearity of the internal electrode layers deteriorates, that is, cracks occur in the internal electrode layers. If the linearity of the internal electrode layers deteriorates, the dielectric constant of the resulting capacitor will decrease, resulting in a decrease in capacitance, which ultimately fails to meet higher capacity and thinner layers.

Second, the price of the sintering furnace is high, and the damage of the used sintering furnace is also serious. The maintenance and management costs of the sintering furnace increase with the use time, and at the same time, the energy cost required for vitrification also increases.

For the above reasons, it is desirable to lower the calcination temperature as much as possible.

On the other hand, if the calcination temperature is too low, densification cannot be achieved during vitrification, and a dielectric ceramic composition having sufficient properties cannot be obtained.

Therefore, it is required to be able to fire at a lower temperature without impairing the densification of the dielectric ceramic composition.

Patent Document 1 Japanese Patent Application Laid-Open No. 60-131708

Contents of the invention

The object of the present invention is to provide a method for producing a dielectric ceramic composition capable of obtaining a dense dielectric ceramic composition without impairing various electrical properties even when fired at a low temperature (for example, 1250° C. or lower), and a product obtained by the method. A dielectric ceramic composition, a method for producing an electronic component such as a chip capacitor using the dielectric ceramic composition as a dielectric layer, and an electronic component obtained by the method.

Solution to the problem

In order to achieve the above object, according to the present invention, a method for manufacturing a dielectric ceramic composition is provided, the dielectric ceramic composition has the structural formula (Ca _x Sr _1-x )O] _m [(Ti _y Zr _1-yz Hf _z ) O ₂ ] a dielectric ceramic composition represented by dielectric oxide, manganese oxide, aluminum oxide, and sintering aids, the symbols x, y, z, and m representing the molar ratio of the composition in the above structural formula are 0.5≤x≤1.0 , 0.01≤y≤0.10, 0<z≤0.20, 0.90≤m≤1.04, characterized in that,

A dielectric porcelain composition is made using a sintering aid having:

With _SiO as the main component, further comprising MO (wherein, M is at least one of Ba, Ca, Sr and Mg), a first glass composition; and

It constitutes a second glass composition including B ₂ O ₃ , Al ₂ O ₃ , ZnO, and SiO ₂ and having an average particle diameter of 1.5 μm or less.

According to the present invention, there is provided a method for producing a dielectric ceramic composition, the dielectric ceramic composition having the structural formula (Ca _x Sr _1-x )O] _m [(Ti _y Zr _1-yz Hf _z )O ₂ ] represents a dielectric oxide, manganese oxide, aluminum oxide, and a dielectric ceramic composition of a sintering aid, and the symbols x, y, z, and m representing the molar ratio of the composition in the above structural formula are 0.5≤x≤1.0, 0.01≤y≤ 0.10, 0<z≤0.20, 0.90≤m≤1.04, characterized in that a sintering aid is used, and the sintering aid has:

With _SiO as the main component, further comprising MO (wherein, M is at least one of Ba, Ca, Sr and Mg), a first glass composition; and

Its composition includes B ₂ O ₃ , Al ₂ O ₃ , ZnO and SiO ₂ , and has a second glass composition with an average particle size of 1.5 μm or less,

and has the following steps:

mixing at least the second glass composition with the initial raw materials prepared for the purpose of obtaining the dielectric oxide to prepare the raw materials before reaction;

The step of reacting the prepared pre-reaction raw materials to obtain a dielectric ceramic composition raw material including the reacted raw materials.

The raw material to be mixed when preparing the pre-reaction raw material may be at least the second glass composition in the sintering aid. It is preferably the first to second glass compositions in the sintering aid, more preferably at least the sintering aid, and most preferably all the raw materials except the above-mentioned specific composition of the dielectric oxide.

At least the second glass composition mixed in the pre-reaction raw material is preferably the total amount of the final composition, but may be a part thereof.

In the present invention, "the method of reacting the raw material before the reaction" includes a solid-phase method (such as a calcination method) and a liquid-phase method. The solid-phase method is to prepare raw materials such as BaCO ₃ , TiO _{2 ,} etc., which are prepared in order to obtain the raw materials of the main component, and weigh a specified amount together with the raw materials of the auxiliary components as needed, mix, calcinate, and pulverize, and obtain the calcined raw materials. Methods. The liquid-phase method includes, for example, an oxalate method, a hydrothermal synthesis method, a sol-gel method, and the like. Among them, it is preferable to use a reacted raw material obtained by a solid-phase method.

Preferably, the above-mentioned second glass composition further contains Na ₂ O.

Preferably, the above-mentioned second glass composition comprises 10 to 35% by weight of B ₂ O ₃ , 5 to 25% by weight of Al ₂ O ₃ , 10 to 60% by weight of ZnO, 0 to 15% by weight of Na ₂ O and 5 to 5% by weight of 35% by weight SiO ₂ .

It is preferred to use a sintering aid having 0.5 to 15 moles of the first glass composition for 100 moles of the dielectric oxide and 0.1 to 10 weight percent of the dielectric oxide for 100 weight percent Second glass composition.

It is preferred to make a dielectric porcelain composition with a sintering aid comprising the formula [(Ca _x Sr _1-x )O] _m [(Ti _y Zr _1-yz Hf _z )O ₂ ] The first glass composition and the second glass composition of dielectric oxide, manganese oxide, and aluminum oxide, the symbols x, y, z, and m representing the composition molar ratio in the above structural formula are 0.5≤x≤1.0, 0.01≤ y≤0.10, 0<z≤020, 0.90≤m≤1.04,

For 100 moles of the dielectric oxide, 0.2 to 5 moles of manganese oxide in terms of MnO, 0.1 to 10 moles of alumina in terms of _Al2O3 , and 0.5 to 15 moles of _the first glass composition,

The second glass composition is contained in an amount of 0.1 to 10% by weight relative to 100% by weight of the dielectric oxide.

It is preferable that the dielectric ceramic composition further contains vanadium oxide, and it is 0 to 2.5 moles (except 0 moles) in terms of V ₂ O ₅ with respect to 100 moles of the dielectric oxide.

Preferably, the dielectric ceramic composition further contains an oxide of a rare earth element in an amount of 0.02 to 1.5 mol in terms of a rare earth element relative to 100 mol of the dielectric oxide.

Preferably, the dielectric ceramic composition further contains at least one oxide of Nb, Mo, Ta, W, and Mg, in terms of 0.02 to 1.5 moles of Nb, Mo, Ta, W, and Mg per 100 moles of the dielectric oxide.

The dielectric porcelain composition is preferably produced at a firing temperature of 1250°C or below.

In the present invention, according to the best mode, a method for producing a dielectric ceramic composition is provided, and the dielectric ceramic composition is produced with the structural formula [(Ca _x Sr _1-x )O] _m [(Ti _y Zr Dielectric oxide represented by _1-yz Hf _z )O ₂ ], manganese oxide, aluminum oxide, vanadium oxide, oxides of rare earth elements, oxides of at least one of Nb, Mo, Ta, W, and Mg, and sintered The dielectric porcelain composition of the auxiliary agent, the symbols x, y, z, and m representing the molar ratio of the composition in the above structural formula are 0.5≤x≤1.0, 0.01≤y≤0.10, 0<z≤020, 0.90≤m≤1.04,

For 100 moles of dielectric oxide, it contains: manganese oxide, converted to MnO _, 0.2 to 5 moles; aluminum oxide, _{converted to Al2O3, 0.1 to 10 moles; vanadium oxide, converted to V2O5 , 0} to 2.5 moles (except 0 moles); oxides of rare earth elements, 0.02 to 1.5 moles in conversion of rare earth elements; oxides of at least one of Nb, Mo, Ta, W and Mg, based on the Nb, Mo, Ta, W 0.02 to 1.5 moles in terms of Mg, characterized in that a sintering aid is used, and the sintering aid has:

A first glass composition having _SiO2 as the main component and further comprising MO (wherein M is at least one of Ba, Ca, Sr and Mg) is 0.5 to 15 moles for 100 moles of the dielectric oxide;

Its composition includes 10-35% by weight of _B2O3 , 5-25% by weight of _Al2O3 , 10-60% by _weight of _ZnO , 0-15% by weight of _Na2O and 5-35% by weight of SiO ₂ , having an average particle size of 1.5 μm or less, relative to 100% by weight of the dielectric oxide, 0.1 to 10% by weight of the second glass composition,

and has the following steps:

mixing at least the second glass composition with the initial raw materials prepared for the purpose of obtaining the dielectric oxide to prepare the raw materials before reaction;

reacting the prepared pre-reaction raw materials to obtain a dielectric ceramic composition raw material comprising the reacted raw materials;

A step of sintering the obtained dielectric ceramic composition raw material at a calcination temperature of 1250° C. or lower to produce a dielectric ceramic composition.

The dielectric particles constituting the dielectric ceramic composition obtained by any of the above methods have an average crystal grain size of 0.8 μm or less. The average crystal grain size is calculated by, for example, a coding method or the like.

The inventors of the present invention have found that by using a sintering aid containing the second glass composition, the average crystal diameter of the dielectric particles constituting the obtained dielectric ceramic composition can be controlled, and as a result, the layer manufactured using the dielectric ceramic composition can be improved. Capacitance of electronic components such as ceramic capacitors.

That is, according to the present invention, there is provided a dielectric ceramic composition having dielectric particles having an average crystal grain size of 0.8 μm or less obtained by any one of the methods described above.

According to the present invention, there is provided a method for manufacturing an electronic component, wherein an electronic component having a dielectric layer composed of a dielectric ceramic composition and an internal electrode layer mainly composed of a base metal is provided, wherein the electronic component is manufactured by any of the above-mentioned methods The dielectric porcelain composition.

According to the present invention, there is provided an electronic component having a dielectric layer made of a dielectric ceramic composition and an internal electrode layer comprising a base metal, wherein the dielectric ceramic composition is the dielectric ceramic according to any one of the above combination.

The electronic components are not particularly limited, but examples include laminated ceramic capacitors, laminated piezoelectric elements, and other surface mount (SMD) chip-type electronic components.

The effect of the invention

The present inventors found that by using a specific glass composition as a sintering aid in addition to the previously used sintering aid, the linearity of the internal electrodes does not deteriorate even when fired at a low temperature of, for example, 1250° C. Various electrical properties are damaged, and dense dielectric ceramic compositions and electronic parts can be obtained. As a result, thinning of the dielectric layer and high capacity of electronic components are achieved.

The dielectric particles constituting the dielectric ceramic composition obtained by this method are finely controlled so that the average crystal particle size is 0.8 μm or less. The inventors of the present invention believe that such a reduction in the average crystal grain size of the dielectric particles contributes to a high capacity.

That is, according to the present invention, there are provided a method for producing a dielectric ceramic composition capable of obtaining a dense dielectric ceramic composition without impairing various electrical properties even when fired at a low temperature, a dielectric ceramic composition obtained by the method, and The dielectric ceramic composition is used as a method for producing electronic components such as chip capacitors as a dielectric layer, and an electronic component obtained by the method.

Brief description of the drawings

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

Detailed ways

Hereinafter, the present invention will be described based on the embodiments shown in the drawings.

As shown in FIG. 1 , a laminated ceramic capacitor 1 according to an embodiment of the present invention has a capacitor element main body 10 composed of dielectric layers 2 and internal electrode layers 3 laminated alternately multiple times. A pair of external electrodes 4 are formed at both end portions of the capacitor element main body 10 , and are electrically connected to the internal electrode layers 3 alternately arranged inside the element body 10 . The shape of the capacitor element main body 10 is not particularly limited, but is usually a rectangular parallelepiped. In addition, the size thereof is not particularly limited, and is usually (0.4-5.6 mm)×(0.2-5.0 mm)×(0.2-1.9 mm).

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

Dielectric layer 2 comprises a dielectric ceramic composition produced by the method of the present invention. The dielectric ceramic composition obtained by the method according to one embodiment of the present invention has at least one of dielectric oxides, manganese oxides, aluminum oxides, vanadium oxides, oxides of rare earth elements, Nb, Mo, Ta, W, and Mg oxide. Furthermore, 17 kinds of elements including Sc, Y, lanthanoids, and the like are included in the rare earth elements.

The dielectric oxide is represented by the structural formula (Ca _x Sr _1-x )O] _m [(Ti _y Zr _1-yz Hf _z )O ₂ ]. The symbols x, y, z, and m representing the composition molar ratio in the formula are 0.5≤x≤1.0 (preferably 0.6≤x≤0.9), 0.01≤y≤0.10 (preferably 0.02≤y≤0.07), 0<z≤ 0.20 (preferably 0<z≤0.10), 0.90≤m≤1.04 (preferably 1.005≤m≤1.025).

The contents of manganese oxide, aluminum oxide, vanadium oxide, oxides of rare earth elements, and oxides of at least one of Nb, Mo, Ta, W, and Mg are as follows.

For 100 moles of dielectric oxide containing:

Manganese oxide, converted to MnO, is 0.2 to 5 moles, preferably 0.2 to 3 moles;

Alumina, converted into Al ₂ O _3, is 0.1 to 10 moles, preferably 0.1 to 5 moles;

Vanadium oxide, converted into _{V2O5 ,} is 0 to 2.5 moles (except 0 moles), preferably 0.5 to 2.5 moles;

Oxides of rare earth elements, in terms of rare earth elements, are 0.02 to 1.5 moles, preferably 0.10 to 1.0 moles;

The oxide of at least one of Nb, Mo, Ta, W, and Mg is 0.02 to 1.5 mol, preferably 0.10 to 1.0 mol, in terms of the Nb, Mo, Ta, W, and Mg.

The dielectric ceramic composition obtained by the method according to one embodiment of the present invention contains a sintering aid. It will be described in detail later.

Various conditions such as the lamination number and thickness of the dielectric layer 2 can be appropriately determined according to the purpose and application, but in this embodiment, the thickness of the dielectric layer 2 is 5 μm or less, preferably 3 μm or less, more preferably as thin as 1 μm or less. . Furthermore, the dielectric layer 2 is composed of crystal grains and grain boundary phases. In the present embodiment, the average crystal grain size of the crystal grains (dielectric particles) of the dielectric layer 2 is preferably 0.8 μm or less, more preferably 0.5 μm or less. Since the average crystal grain size is miniaturized, it is easy to cope with thinner layers of products, and as a result, higher capacity can be realized. The grain boundary phase usually contains oxides of raw materials constituting dielectric materials or internal electrode materials, oxides of additional raw materials, and oxides of other raw materials mixed in as impurities as components, and is usually composed of glass or vitreous.

The conductive material contained in the internal electrode layer 3 is not particularly limited, but an inexpensive base metal can be used so that the constituent material of the dielectric layer 2 has reduction resistance. As the base metal used as the conductive material, Ni or a Ni alloy is preferable. The Ni alloy is preferably an alloy of one or more elements selected from Mn, Cr, Co, and Al and Ni, and the Ni content in the alloy is preferably 95% by weight or more. Furthermore, various trace components such as P, Fe, and Mg may be contained in Ni or the Ni alloy in an amount of 0.1% by weight or less. The thickness of the internal electrode layer can be appropriately determined depending on the application and the like, but is usually 0.5 to 5 μm, particularly preferably 1 to 2.5 μm.

The conductive material contained in the external electrodes 4 is not particularly limited, but generally Cu and Cu alloys or Ni and Ni alloys are used. Furthermore, Ag and Ag-Pd alloys and the like can also be used. Also, in this embodiment, inexpensive Ni, Cu, and alloys thereof are used. The thickness of the external electrodes can be appropriately determined depending on the application and the like, but is generally preferably about 10 to 50 μm.

The laminated ceramic capacitor 1 produced by the method for producing a dielectric ceramic composition according to the present invention is formed into a green sheet by a normal printing method using a paste or a thin layer method, as in a conventional laminated ceramic capacitor, and the After it is sintered, it is made by printing or copying the external electrodes and then sintering. Hereinafter, the manufacturing method will be specifically described.

First, pastes for dielectric layers, pastes for internal electrodes, and pastes for external electrodes were produced, respectively.

When producing a paste for a dielectric layer, first, a dielectric ceramic composition raw material contained therein is prepared. The dielectric ceramic composition raw materials contain main component raw materials and auxiliary component raw materials.

As the main component raw material, the dielectric oxide having the above composition was used.

Manganese oxide and/or a compound that becomes manganese oxide after sintering, alumina and/or a compound that becomes alumina after sintering, vanadium oxide and/or a compound that becomes vanadium oxide after sintering, and oxides of rare earth elements are used as auxiliary component raw materials And/or become the compound of the oxide of rare earth element after sintering, the oxide of at least one in Nb, Mo, Ta, W and Mg and/or become at least one in Nb, Mo, Ta, W and Mg after sintering Kinds of oxide compounds and sintering aids.

In the present invention, a specific sintering aid is used. The sintering aid contains a first glass composition and a second glass composition.

The first glass composition is a component for promoting the degree of sintering during sintering.

The first glass composition has SiO ₂ as a main component and further contains MO (wherein M is at least one of Ba, Ca, Sr, and Mg). Preferably, _SiO2 is used as the main component, and one or both of BaO and CaO are also included.

The first glass composition mainly functions as a sintering aid, but also has the effect of improving the defect rate of initial insulation resistance (IR) when the dielectric layer 2 is thinned. More preferably, the first glass composition contains a composite oxide (hereinafter also referred to as BCG) represented by the composition formula {(Ba _w , Ca _1-w )O} _v SiO ₂ . Since the composite oxide {(Ba _w , Ca _1-w )O} _v SiO ₂ has a low melting point, it has good reactivity with the main component raw materials. In the preferred composition formula {(Ba _w , Ca _1-w )O} _v SiO ₂ , the symbol v representing the composition molar ratio in the composition formula is preferably 0.5≤v≤4.0, more preferably 0.55≤ v≤3.0. If v is too small, that is, if there is too much SiO ₂ , it will react with the main component and deteriorate the dielectric properties. On the other hand, if v is too large, the melting point becomes high and the degree of sintering deteriorates, which is unfavorable. Furthermore, the symbol w representing the compositional molar ratio of Ba and Ca is arbitrary (0≤w≤1), and may contain only one of them, but is preferably 0.5≤w≤1.

The melting point of the first glass composition is preferably 1150°C or lower, more preferably 900˜1100°C. Low melting point makes it easy to sinter at low temperature.

The content of the first glass composition is 0.5 to 15 mol, preferably 0.5 to 10 mol, more preferably 0.5 to 5 mol, based on 100 mol of the dielectric oxide. Adding a small amount of the first glass composition can effectively reduce the occurrence of the initial IR failure rate, but conversely, if it is too much, the dielectric constant decreases, and there is a possibility that sufficient capacitance cannot be secured.

The second glass composition is a component for increasing reactivity (for example, pseudo-firing reactivity) between raw materials before sintering, for example, during firing. As a result, there is an advantage that subsequent sintering can be performed at a relatively low temperature.

The second glass composition contains at least B ₂ O ₃ , Al ₂ O ₃ , ZnO and SiO ₂ , and preferably further contains Na ₂ O.

The ratio of these oxides in the second glass composition is:

B ₂ O ₃ , 10-35% by weight, preferably 15-30% by weight;

Al ₂ O ₃ , 5-25% by weight, preferably 10-20% by weight;

ZnO, 10-60% by weight, preferably 20-45% by weight;

SiO ₂ , 5 to 35% by weight, preferably 10 to 20% by weight.

The ratio of Na ₂ O in the case of containing Na ₂ O is 0 to 15% by weight (excluding 0% by weight), preferably 0.001 to 2% by weight.

The second glass composition has an average particle diameter of 1.5 μm or less, preferably 1 μm or less. If the average particle size is too large, the dispersibility of the second glass composition will decrease, which will hinder uniform sintering.

Oxides other than the above-mentioned oxides may also be contained in the second glass composition within a range not contrary to the object of the present invention.

The melting point of the second glass composition is preferably 650°C or lower, more preferably 580˜650°C. Low melting point makes it easy to sinter at low temperature.

The content of the second glass composition is 0.1 to 10% by weight, preferably 0.1 to 3% by weight relative to 100% by weight of the dielectric oxide. If the amount of the second glass composition added is too small, the sintering at low temperature tends to be insufficient, and if it is too large, the average crystal grain size of the dielectric particles is not uniform due to the separation of the second glass composition, and there is a temperature characteristic. tendency to deteriorate.

In this embodiment, when the main component raw materials are produced by the solid-phase method, the liquid-phase method, etc., the mixture obtained by mixing is reacted under predetermined conditions to obtain the dielectric ceramic composition raw material (pre-added), and the mixture is mixed at least for the second Two glass compositions (preferably the first to second glass compositions in the sintering aid, more preferably at least the sintering aid (comprising the first glass composition and the second glass composition), most preferably comprising the sintering aid All auxiliary ingredients of the agent).

Hereinafter, a case where a dielectric ceramic composition is obtained by mixing all the auxiliary component raw materials when producing the main component raw materials by a solid-state method (such as a calcination method) will be described as an example.

_First , _a predetermined amount _{, such as MnCO 3 , Al 2 O 3} , V ₂ Auxiliary component raw materials such as O ₅ , Y ₂ O ₃ , first glass composition, second glass composition, and if necessary, other auxiliary component raw materials are also weighed, mixed and dried to prepare the final composition before firing. raw material.

Next, calcining the prepared pre-calcining powder. Calcination conditions are not particularly limited, but can be performed under the conditions shown below. In particular, in this embodiment, since the second glass composition is contained in the raw material before firing, the firing reaction can be sufficiently promoted even if the firing is performed at a low temperature of, for example, 1100°C or lower, preferably 900 to 1100°C. sex. The rate of temperature increase under other calcination conditions is preferably 50 to 400°C/hour, more preferably 100 to 300°C/hour. The holding time of the calcination temperature is preferably 0.5 to 6 hours, more preferably 1 to 3 hours. The treatment atmosphere may be any one of air, nitrogen and reducing atmosphere. Moreover, it is also possible to perform calcination multiple times.

Next, the fired calcined powder is pulverized with an alumina roll or the like, and then dried to obtain a dielectric ceramic composition raw material (powder).

Next, this dielectric ceramic composition raw material was made into a coating, and the paste for dielectric layers was prepared. The paste for the dielectric layer may be an organic paint obtained by kneading the raw material of the dielectric ceramic composition and an organic vehicle, or may be a water-based paint.

As the raw material of the dielectric ceramic composition, the above-mentioned oxides and their mixtures and composite oxides can be used, but in addition, various compounds such as carbonates, After appropriately selecting from oxalate, nitrate, hydroxide, organometallic compound, etc., it is used after mixing. The content of each compound in the raw material of the dielectric ceramic composition can be determined so that the composition of the above-mentioned dielectric ceramic composition can be obtained after sintering.

The particle size of the dielectric ceramic composition powder in the state before coating is usually 0.1 to 3 μm in average particle size.

The organic vehicle is a substance in which the binder is dissolved in an organic solvent. The binder used for the organic medium is not particularly limited, and can be appropriately selected from various common binders such as ethyl cellulose and polyvinyl butyral. In addition, the organic solvent used is not particularly limited, and can be appropriately selected from various organic solvents such as terpineol, diethylene glycol monobutyl ether, acetone, and toluene according to the methods utilized such as printing method and thin layer method.

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

Conductive materials composed of various conductive metals and alloys, or various oxides, organic metal compounds, resinates, etc. that constitute the above-mentioned conductive materials after sintering are mixed with the above-mentioned organic media to prepare internal electrodes. paste.

The paste for external electrodes was also prepared in the same manner as the paste for internal electrodes.

When using the printing method, the paste for the dielectric layer and the paste for the internal electrode layer are laminated and printed on a substrate such as polyethylene terephthalate, cut into a predetermined shape, and then peeled off from the substrate to form a green sheet. . On the other hand, when the thin layer method is used, a green substrate is formed using a dielectric layer paste, and the internal electrode paste is printed thereon, and then laminated to form a green sheet.

Next, before sintering, the green sheet is subjected to a binder removal process. The debinder treatment can be performed under normal conditions, but in the case of using base metals such as Ni and Ni alloys as the conductive material of the internal electrode layer, it is preferable to heat up at a rate of 5 to 300°C/hour, especially 10 to 100°C. °C/hour, retention temperature: 180-400 °C, especially 200-300 °C, temperature retention time: 0.5-24 hours, especially 5-20 hours, atmosphere: in air.

The atmosphere at the time of sintering the green sheet can be appropriately determined according to the type of conductive material in the paste for internal electrodes, but when using base metals such as Ni and Ni alloys as the conductive material, the partial pressure of oxygen in the sintering atmosphere is preferably set to 10 ^-7 ~ 10 ^-3 Pa. If the partial pressure of oxygen is less than the above-mentioned range, abnormal sintering of the conductive material of the internal electrode layer will occur, resulting in cracking. In addition, if the oxygen partial pressure exceeds the above-mentioned range, there is a tendency for the internal electrode layer to be oxidized.

Within the range where the green sheet can be sufficiently densified without causing electrode cracking due to abnormal sintering of the internal electrode layer, deterioration of capacitance temperature characteristics due to diffusion of internal electrode layer constituting materials, or reduction of the dielectric ceramic composition, The retention temperature at the time of sintering is appropriately determined. This is because if the sintering temperature is too low, the green sheet is not dense, and if the sintering temperature is too high, internal electrode cracks (linear deterioration), capacitance temperature characteristics deterioration due to diffusion of conductive materials, or dielectric reduction occur.

Conventionally, in order to sufficiently densify a raw thin green sheet made of a CaSr-ZrTi-Mn-based material, it was necessary to sinter at 1300°C or higher. Even a green sheet comprising a CaSr-ZrTi-Mn-based material can be calcined at a low temperature of preferably 1250°C or lower, more preferably 1230°C or lower. In this way, damage to the sintering furnace can be prevented, maintenance and management costs or energy costs can be effectively suppressed, and troubles such as occurrence of cracks and lowering of the dielectric constant can be prevented. Also, the lower limit of the calcination temperature is preferably about 950°C, more preferably about 1000°C.

As other calcination conditions, it is preferable to set the heating rate at 50 to 500° C./hour, more preferably 200 to 300° C./hour, and to set the temperature holding time at 0.5 to 8 hours, more preferably 1 to 8 hours. For 3 hours, the cooling rate is set to 50 to 500°C/hour, more preferably 200 to 300°C/hour. In addition, the firing atmosphere is preferably a reducing atmosphere, and as the gas in the atmosphere, for example, a mixed gas of N ₂ and H ₂ is preferably used after being humidified.

When firing in a reducing atmosphere, it is preferable to anneal the sintered body (capacitor element main body) after sintering. Annealing is a treatment for re-oxidizing the dielectric layer, and by doing so, the IR lifetime can be significantly increased, thereby improving reliability.

The oxygen partial pressure in the annealing atmosphere is preferably 1×10 ^-4 Pa or higher, particularly preferably 1×10 ^-4 to 10 Pa. If the oxygen partial pressure is less than the above range, reoxidation of the dielectric layer becomes difficult, and if it exceeds the above range, the internal electrode layer tends to be oxidized.

The retention temperature during annealing is preferably 1200°C or lower, particularly preferably 500 to 1200°C. If the holding temperature is lower than the above-mentioned range, the oxidation of the dielectric layer is not sufficient, so the IR becomes low, and the IR life tends to be shortened. On the other hand, if the retention temperature exceeds the above range, not only the capacitance will decrease after the internal electrode is oxidized, but also the internal electrode will react with the dielectric, which will easily cause the deterioration of the capacitance temperature characteristics, the decrease of IR, and the decrease of IR life. Furthermore, the annealing step may only consist of a temperature rising process and a temperature falling process. That is, the temperature holding time may be set to zero. In this case, the retention temperature corresponds to the maximum temperature.

As other annealing conditions, the temperature holding time is preferably 0 to 20 hours, more preferably 2 to 10 hours, and the cooling rate is 50 to 500°C/hour, more preferably 100 to 300°C /Hour. In addition, as the gas in the annealing atmosphere, for example, humidified N ₂ gas or the like is preferably used.

In the above-mentioned binder removal treatment, sintering and annealing, to humidify _N2 gas and mixed gas, etc., for example, a humidifier etc. can be used. In this case, the water temperature is preferably 5 to 75°C.

Debinder treatment, sintering and annealing can be performed sequentially or independently. In the case of continuous operation, it is preferable to change the atmosphere without cooling after the binder removal treatment, then raise the temperature to the hold temperature for sintering to perform sintering, then cool, and when the hold temperature for annealing is reached, change the atmosphere to perform annealing. On the other hand, when it is carried out independently, it is preferable that during sintering, after the temperature is raised to the holding temperature during the binder removal treatment under N _gas or humidified _N gas atmosphere, the temperature is further increased after changing the atmosphere, preferably in After cooling to the retention temperature during annealing, the atmosphere was changed to N ₂ gas or humidified N ₂ gas atmosphere again, and cooling was continued. In addition, during the annealing, the atmosphere may be changed after the temperature is raised to the retention temperature under the N ₂ gas atmosphere, or the entire annealing process may be set in a humidified N ₂ gas atmosphere.

The capacitor sintered body obtained as described above is subjected to end surface grinding by, for example, barrel grinding and sandblasting, and the paste for external electrodes is printed or copied, and then fired to form external electrodes 4 . The firing conditions of the paste for external electrodes are, for example, preferably in a humidified mixed gas of nitrogen and hydrogen at 600 to 800° C. for about 10 minutes to 1 hour. Then, if necessary, a covering layer (liner layer) is formed on the surface of the external electrode 4 by plating or the like.

The ceramic capacitor of the present embodiment manufactured in this way is mounted on a printed circuit board by soldering or the like, and is used in various electronic devices and the like.

As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment, Various deformation|transformation is possible in the range which does not deviate from the summary of this invention.

For example, the dielectric ceramic composition obtained by the method according to the present invention can be used not only for laminated ceramic capacitors but also for other electronic components in which dielectric layers are formed.

Example

Hereinafter, more specific examples are given to further describe the present invention in detail. However, the present invention is not limited only to these examples.

Example 1

Modulation of Dielectric Raw Materials

First, SrCO ₃ , CaCO ₃ , TiO ₂ , ZrO _{2 ,} and HfO ₂ with an average particle diameter of 0.4 μm were prepared as starting materials for preparing the main component raw materials.

Next, each of the prepared initial raw materials was weighed according to the atomic ratio of the final composition [Ca _0.7 Sr _0.3 ]O][((Ti _0.05 Zr _0.9 Hf _0.05 )O ₂ ].

Next, 1 mol of MnCO ₃ , 0.5 mol of Al ₂ O ₃ , and 3 mol of (Ba _0.6 Ca _0.4 )SiO ₃ (BCG) were added as the first glass to a total of 100 mol of the weighed starting materials. combination. In addition, a specific weight % of B-Al-Zn-Si-based glass frit was added as a second glass composition to a total of 100% by weight of each starting material after weighing, and a powder before firing was obtained after the addition.

Next, the obtained pre-calcination powder was calcined. Calcination conditions are as follows. Heating rate: 200°C/hour, holding temperature: 1100°C, temperature holding time: 2 hours, atmosphere: in air.

Next, the calcined material was pulverized with an alumina roll to form a calcined powder, and a dielectric raw material (dielectric ceramic composition raw material (powder)) composed of the calcined powder was obtained.

In this example, as shown in Table 1, the average particle diameter and the addition amount of the B-Al-Zn-Si-based glass frit were changed for each sample. In addition, as the B-Al-Tn-Si-based glass frit, 25% by weight of B ₂ O ₃ , 25% by weight of ZnO, 25% by weight of SiO ₂ , 15% by weight of Al ₂ O ₃ , 10% by weight Composed of Na ₂ O and having a softening point of 600°C.

Moreover, by wet mixing BaCO ₃ , CaCO ₃ and SiO ₂ by a ball mill for 16 hours, drying, sintering in air at 1000-1300°C, and wet pulverization by a ball mill for 100 hours, (Ba _0.6 Ca _0.4 )SiO ₃ .

Next, using the obtained dielectric material, the following disk-shaped samples and capacitor samples were produced for each sample.

Fabrication of disc-shaped samples

First, 0.6% by weight of polyvinyl alcohol was added as a binder to the obtained dielectric material, and the binder and the dielectric material were mixed into pellets. Then, 0.3 g of this granular dielectric raw material was weighed and pressed at a pressure of 1.3 ton/cm ² to obtain a disk-shaped compact with a diameter of 1 mm and a thickness of 0.7 mm.

Next, the obtained disc-shaped compact was subjected to binder removal treatment, sintering, and annealing to obtain a disc-shaped sintered compact with a diameter of about 10 mm and a thickness of about 0.5 mm. The binder removal treatment was carried out under the conditions of a heating time of 200° C./hour, a holding temperature of 400° C., a holding time of 2 hours, and an air atmosphere. In addition, at a heating rate of 200°C/hour, retention temperature: refer to Table 1, retention time of 2 hours, cooling rate of 200°C/hour, humidified N ₂ +H ₂ mixed gas atmosphere (oxygen partial pressure 10 ^-12 Pa) conditions for sintering. Annealing was performed under conditions of a retention temperature of 1100°C, a temperature retention time of 2 hours, a cooling rate of 200°C/hour, and a humidified N ₂ gas atmosphere (oxygen partial pressure 10 ^-2 Pa). In addition, a humidifier was used to humidify the atmospheric gas during sintering and annealing.

Next, by coating In-Ga alloy on both surfaces of the obtained disc-shaped sintered body, an electrode having a diameter of 6 mm was formed, and a disc-shaped sample was produced.

Fabrication of capacitor samples

100 parts by weight of the obtained dielectric material, 4.8 parts by weight of acrylic resin, 40 parts by weight of methylene chloride, 20 parts by weight of ethyl acetate, 6 parts by weight of mineral turpentine, and 4 parts by weight of acetone were mixed with a ball mill to make a paste. Paste for dielectric layer.

100 parts by weight of Ni particles with an average particle diameter of 0.1-0.8 μm, 40 parts by weight of organic vehicle (8 parts by weight of ethyl cellulose dissolved in 92 parts by weight of diethylene glycol monobutyl ether) and 40 parts by weight of diethylene glycol were kneaded by three rolls. 10 parts by weight of alcohol monobutyl ether was made into a paste to obtain a paste for internal electrode layers.

100 parts by weight of Cu particles with an average particle diameter of 0.5 μm, 35 parts by weight of an organic vehicle (8 parts by weight of ethyl cellulose dissolved in 92 parts by weight of diethylene glycol monobutyl ether) and 7 parts by weight of diethylene glycol monobutyl ether were kneaded. parts by weight, and made into a paste to obtain a paste for external electrodes.

Next, a green substrate with a thickness of 7 μm was formed on a PET film using the above-mentioned paste for a dielectric layer, and after printing the paste for an internal electrode layer thereon, the green substrate was peeled off from the PET film.

Next, these green substrates and a protective green substrate (a green substrate on which the paste for internal electrode layers was not printed) were laminated and pressure-bonded to obtain a green sheet. The number of laminations of substrates having internal electrodes was set to 5 layers.

Next, the green sheet was cut into a predetermined size, and subjected to binder removal treatment, sintering, and annealing (all under the same conditions as those for the disk-shaped sample) to obtain a laminated porcelain sintered body.

Next, after polishing the end face of the laminated ceramic sintered body with a sand blaster, the paste for external electrodes was copied on the end face, and fired at 800°C for 10 minutes in a humidified N ₂ +H ₂ atmosphere to form the external electrodes. , samples of laminated ceramic capacitors with the structure shown in Fig. 1 were obtained. The size of each sample thus obtained was 3.2 mm×1.6 mm×0.6 mm, the number of dielectric layers sandwiched between the internal electrode layers was 4, the thickness thereof was 4.9 μm, and the thickness of the internal electrode layers was 0.2 μm.

Evaluation of Disc Samples and Capacitor Samples

Using the obtained disk-shaped samples and capacitor samples, evaluations of ceramic properties (sintered density) and electrical properties (insulation resistance IR) were performed. In addition, the average crystal particle diameter of the dielectric particles was measured. The results are shown in Table 1.

Porcelain characteristics (sintered density) were evaluated as follows. Calculated from the size and mass of the disk-shaped sample, the sintered density is preferably 4.5 g/cm ³ . Furthermore, the value of the sintered density was calculated|required from the average value of the measured value using the disc-shaped sample number n=10.

The electrical characteristics (insulation resistance IR) were evaluated as follows. For the capacitor sample, the insulation resistance IR (unit: Ω) after applying DC50V for 60 seconds at 25° C. was measured for the capacitor sample using an insulation resistance meter (R8340A manufactured by Adban Test Co., Ltd.). The insulation resistance IR is preferably 1×10 ¹¹ Ω or more. Furthermore, the value of the insulation resistance IR was calculated|required from the average value of the measured value using capacitor sample number n=10. Table 1 shows the results.

The average crystal grain size of the dielectric particles (grains) constituting the dielectric layer was calculated by the coding method using the SEM photograph of the capacitor sample. In this embodiment, the shape of the dielectric particles is assumed to be spherical, and the particle size is conveniently calculated. Specifically, first, using an SEM photograph showing the fine structure of the dielectric layer, an arbitrary straight line is drawn on the SEM photograph, and the number of intersecting grain boundaries (intersection points) between dielectric particles adjacent to the line is obtained. . Next, the number of intersections PL with grain boundaries per unit length is calculated from the obtained number of intersections. Next, the code length L3 is calculated using the obtained value of PL. The code length L3 is obtained by 1/PL. Next, the obtained value of L3 was multiplied by 1.5, that is, L3×1.5, to calculate the average crystal grain size of the dielectric particles. Furthermore, assuming that the field of view of the SEM photographs used is 23 μm×30 μm, 5 to 6 photographs are used for each sample, and the respective particle diameters are calculated, and these average values are defined as the average crystal grain diameter. Table 1 shows the results.

In addition, in Table 1, "m*10 ⁿ " means "m×10 ⁿ " among the numerical values of the insulation resistance IR.

Table 1

From Table 1, the following matters can be understood. As in Sample 1, if the second glass composition was not included as a sintering aid, sufficient sintering density could not be obtained when sintering at a low temperature of 1250° C. or lower, and the insulation resistance decreased. "-" in the insulation resistance column of sample 1 indicates that the sintered density was too low to densify, and the insulation resistance could not be measured.

Like samples 2 to 3, in order to obtain a sufficient sintered density without the second glass composition, when the sintering temperature rises above 1250°C, the insulation resistance disappears, but the linearity of the internal electrodes deteriorates, and, Since the average crystal grain size of the dielectric particles is too large, the thickness cannot be reduced, and as a result, the capacity cannot be increased.

Like sample 8, if the addition amount of the second glass composition is too much, then in the case of sintering at low temperature, sufficient sintering density is obtained, and the insulation resistance also disappears, but because the average crystal grain size of the dielectric particles is too large, Therefore, the thickness cannot be reduced, and as a result, the capacity cannot be increased.

As in sample 10, if the average particle size of the second glass composition used is too large, sufficient sintered density cannot be obtained in the case of sintering at low temperature. The "-" in the column of the insulation resistance of the sample 10 is the same as that of the sample 1.

In this regard, as in samples 4 to 7, 9, 11, and 12, by adding an appropriate amount of the second glass composition with an appropriate average particle size, sufficient sintered density can be obtained even when sintered at a low temperature, and the dielectric particle The average crystal grain size is also finer, and sufficient insulation resistance is obtained.

Example 2

As the B-Al-Zn-Si-based glass frit, except that Na ₂ O is not used, 25% by weight of B ₂ O ₃ , 25% by weight of ZnO, 25% by weight of SiO ₂ , and 25% by weight of Al ₂ O ₃ and having a softening point of 650° C., a disk-shaped sample and a capacitor sample were produced in the same manner as in Sample 6 of Example 1, and evaluated in the same manner (Sample 13). Table 2 shows the results.

Table 2

As shown in Table 2, it is considered that, as the second glass composition, B-Al-Zn-Si-based glass frit that does not contain Na ₂ O is used, as in the case of sample 6, and sintered at a low temperature. The density was not greatly reduced, and the average crystal particle size of the dielectric particles was also suitable, and good insulation resistance was obtained.

Example 3

As the B-Al-Zn-Si glass frit, in addition to using 35% by weight of B ₂ O ₃ , 10% by weight of ZnO, 35% by weight of SiO ₂ , 5% by weight of Al ₂ O ₃ , and 5% by weight of Disc-shaped samples and capacitor samples were produced in the same manner as in Sample 6 of Example 1, except that they were composed of Na ₂ O and had a softening point of 610° C., and were evaluated in the same manner. As a result, the same result was obtained. In addition, this Example is an example of the case where the composition of a glass frit falls within the optimum range of this invention.

Reference example 1

As the B-Al-Zn-Si glass frit, in addition to using 10% by weight of B ₂ O ₃ , 70% by weight of ZnO, 2% by weight of SiO ₂ , 5% by weight of Al ₂ O ₃ , and 13% by weight of Disc-shaped samples and capacitor samples were produced in the same manner as in Sample 6 of Example 1, except that they were composed of Na ₂ O and had a softening point of 630° C., and were evaluated in the same manner. As a result, it was confirmed that the degree of sintering tended to deteriorate. In addition, this Example is an example when the composition of a glass frit deviates from the optimum range of this invention.

Claims (20)

1. A method for producing a dielectric ceramic composition having a dielectric oxide represented by the structural formula [(Ca _x Sr _1-x )O] _m [(Ti _y Zr _1-yz Hf _z )O ₂ ] material, manganese oxide, aluminum oxide, sintering aid, the symbols x, y, z, m representing the composition molar ratio in the above structural formula are 0.5≤x≤1.0, 0.01≤y≤0.10, 0<z≤0.20, 0.90≤m ≤1.04, it is characterized in that in this method, the following sintering aid is used to manufacture the dielectric ceramic composition, and the sintering aid has: A first glass composition containing _SiO2 as the main component and containing MO, wherein M is at least one of Ba, Ca, Sr and Mg; and It constitutes a second glass composition including B ₂ O ₃ , Al ₂ O ₃ , ZnO, and SiO ₂ and having an average particle diameter of 1.5 μm or less. 2. The method for producing a dielectric ceramic composition according to claim 1, wherein the second glass composition further contains _Na2O . 3. The method for producing a dielectric ceramic composition according to claim 1, wherein the second glass composition contains 10 to 35% by weight of B ₂ O ₃ , 5 to 25% by weight of Al ₂ O ₃ , 10-60% by weight of ZnO and 5-35% by weight of SiO ₂ . 4. The method for producing a dielectric ceramic composition according to claim 2, wherein the second glass composition comprises 10 to 35% by weight of B ₂ O ₃ , 5 to 25% by weight of Al ₂ O ₃ , 10-60% by weight of ZnO, 0-15% by weight of Na ₂ O except 0% by weight, and 5-35% by weight of SiO ₂ . 5. The manufacturing method of the dielectric ceramic composition according to claim 1 or 2, wherein the following sintering aid is used, and the sintering aid has: 0.5-15 moles of the first glass composition relative to 100 moles of the dielectric oxide; 0.1 to 10% by weight of the second glass composition relative to 100% by weight of the dielectric oxide. 6. A method for producing a dielectric ceramic composition having a dielectric oxide represented by the structural formula [(Ca _x Sr _1-x )O] _m [(Ti _y Zr _1-yz Hf _z )O ₂ ] material, manganese oxide, aluminum oxide, sintering aid, the symbols x, y, z, m representing the composition molar ratio in the above structural formula are 0.5≤x≤1.0, 0.01≤y≤0.10, 0<z≤0.20, 0.90≤m ≤1.04, characterized in that the method uses a sintering aid and comprises the steps, the sintering aid having: A first glass composition having _SiO2 as the main component and containing MO, wherein M is _at least one of Ba, Ca, Sr and Mg; and _its composition includes _B2O3 , _Al2O3 , ZnO and SiO ₂ , the second glass composition having an average particle size of 1.5 μm or less, The steps are: mixing at least the second glass composition with the initial raw materials prepared for the purpose of obtaining the dielectric oxide to prepare the raw materials before reaction; The step of reacting the prepared pre-reaction raw materials by a solid phase reaction method to obtain a dielectric ceramic composition raw material containing the reacted raw materials. 7. The manufacture method of the dielectric ceramic composition as described in any one of claim 1,2,6, said ceramic composition has structural formula [(Ca _x Sr _1-x )O] _m [(Ti _y Zr _1-yz Hf _z )O ₂ ] represented dielectric oxide, manganese oxide, aluminum oxide, sintering aid containing the first glass composition and the second glass composition, the symbols x and y representing the composition molar ratio in the above structural formula , z, m are 0.5≤x≤1.0, 0.01≤y≤0.10, 0<z≤0.20, 0.90≤m≤1.04, In addition, _the ceramic composition contains 0.2 to 5 moles of manganese oxide in terms of MnO, 0.1 to 10 moles of alumina in terms of _Al2O3 , and a content of the first glass composition relative to 100 moles of the dielectric oxide. 0.5 to 15 moles relative to 100 moles of dielectric oxide, And the ceramic composition further contains 0.1-10 wt% of the second glass composition relative to 100 wt% of the dielectric oxide. 8. The method for producing a dielectric ceramic composition according to claim 7, wherein the dielectric ceramic composition further contains vanadium oxide, which is 0 to 2.5 moles in terms of V ₂ O ₅ relative to 100 moles of the dielectric oxide , except for 0 moles. 9. The method for producing a dielectric ceramic composition according to claim 7, wherein the dielectric ceramic composition further contains an oxide of a rare earth element, which is 0.02 to 1.5 in terms of a rare earth element relative to 100 moles of the dielectric oxide. Moore. 10. The manufacture method of dielectric ceramic composition as claimed in claim 7, wherein the dielectric ceramic composition also contains the oxide compound of at least one in Nb, Mo, Ta, W and Mg, and it is oxidized with respect to 100 moles dielectric Matter, calculated as Nb, Mo, Ta, W and Mg, is 0.02 to 1.5 moles. 11. The method for producing a dielectric ceramic composition according to any one of claims 1, 2, and 6, wherein the dielectric ceramic composition is sintered at a sintering temperature of 900-1250°C. 12. A method for producing a dielectric ceramic composition having a dielectric oxide represented by the structural formula [(Ca _x Sr _1-x )O] _m [(Ti _y Zr _1-yz Hf _z )O ₂ ] material, manganese oxide, aluminum oxide, vanadium oxide, oxides of rare earth elements, oxides of at least one of Nb, Mo, Ta, W and Mg, and sintering aids. In the above structural formula, the symbol x representing the composition molar ratio, y, z, m are 0.5≤x≤1.0, 0.01≤y≤0.10, 0<z≤0.20, 0.90≤m≤1.04, Among them, relative to 100 moles of dielectric oxides, there are 0.2 to 5 moles of manganese oxide converted into MnO; _0.1 to ₁₀ moles of aluminum oxide converted into _{Al2O3 ;} Vanadium, except 0 moles; oxides of rare earth elements with 0.02 to 1.5 moles converted to rare earth elements; 0.02 to 1.5 moles of Nb, Mo, Ta, W and Mg converted to said Nb, Mo, Ta, W and Mg an oxide of at least one of, The sintering aid has: A first glass composition having _SiO2 as the main component and containing MO, wherein M is at least one of Ba, Ca, Sr and Mg; it is 0.5 to 15 moles relative to 100 moles of the dielectric oxide; and Its composition includes 10-35% by weight of _B2O3 , 5-25% by weight of _Al2O3 , 10-60% by _weight of _ZnO , 0-15% by weight of _Na2O and 5-35% by weight of SiO _2. The second glass composition having an average particle size of 1.5 μm or less, which is 0.1 to 10% by weight relative to 100% by weight of the dielectric oxide, The method also includes the steps of: mixing at least the second glass composition with the initial raw materials prepared for the purpose of obtaining the dielectric oxide to prepare the raw materials before reaction; reacting the prepared pre-reaction raw materials by a solid phase reaction method to obtain a dielectric ceramic composition raw material containing the reacted raw materials; The step of sintering the obtained dielectric ceramic composition raw material at a sintering temperature of 900-1250° C. to manufacture the dielectric ceramic composition. 13. A dielectric ceramic composition having a dielectric oxide represented by the structural formula [(Ca _x Sr _1-x )O] _m [(Ti _y Zr _1-yz Hf _z )O ₂ ], Manganese, aluminum oxide, vanadium oxide, oxides of rare earth elements, oxides of at least one of Nb, Mo, Ta, W and Mg, sintering aids, and the symbols x, y, and z representing the composition molar ratio in the above structural formula , m is 0.5≤x≤1.0, 0.01≤y≤0.10, 0<z≤0.20, 0.90≤m≤1.04, Wherein relative to 100 moles of dielectric oxide, containing Manganese oxide converted to 0.2 to 5 moles of MnO; 0.1-10 moles of alumina converted _{into Al2O3} ; Vanadium oxide converted into V ₂ O ₅ is 0 to 2.5 moles, except 0 moles; Oxides of rare earth elements with 0.02 to 1.5 moles of rare earth elements converted into rare earth elements; An oxide of at least one of Nb, Mo, Ta, W, and Mg in terms of 0.02 to 1.5 moles in terms of the Nb, Mo, Ta, W, and Mg, The dielectric ceramic composition is made using a sintering aid having: a first glass composition having _SiO2 as the main component and containing MO, wherein M is at least one of Ba, Ca, Sr and Mg; and It constitutes a second glass composition comprising B ₂ O ₃ , Al ₂ O ₃ , ZnO and SiO ₂ , the average particle size of the second glass composition before sintering is 1.5 μm, The average particle diameter of the dielectric particles constituting the sintered dielectric layer is 0.8 μm or less. 14. The dielectric ceramic composition according to claim 13, wherein the second glass composition further comprises _Na2O . 15. The dielectric ceramic composition according to claim 13, wherein the second glass composition comprises 10 to 35% by weight of B ₂ O ₃ , 5 to 25% by weight of Al ₂ O ₃ , 10 to 60% by weight ZnO and 5-35 wt% SiO ₂ . 16. The dielectric ceramic composition according to claim 14, wherein the second glass composition comprises 10 to 35% by weight of B ₂ O ₃ , 5 to 25% by weight of Al ₂ O ₃ , 10 to 60% by weight ZnO, 0-15 wt% but 0 wt% Na ₂ O and 5-35 wt% SiO ₂ . 17. The dielectric ceramic composition according to claim 13, wherein the dielectric ceramic composition uses a sintering aid having: 0.5-15 moles of the first glass composition relative to 100 moles of the dielectric oxide; 0.1 to 10% by weight of the second glass composition relative to 100% by weight of the dielectric oxide. 18. The dielectric ceramic composition according to claim 13, wherein said dielectric ceramic composition is sintered at a sintering temperature of 900-1250°C. 19. A method for producing an electronic component having a dielectric layer composed of a dielectric ceramic composition and an internal electrode layer mainly composed of a base metal, wherein the dielectric ceramic composition A dielectric ceramic composition manufactured by any one of claims 1, 2, and 6. 20. An electronic component having a dielectric layer composed of a dielectric ceramic composition and an internal electrode layer containing a base metal, wherein the dielectric ceramic composition is the dielectric ceramic composition according to claim 13.