JP2020161777A - Internal electrode conductive paste, ceramic electronic component, and multilayer ceramic capacitor - Google Patents

Abstract

To provide an internal electrode conductive paste which can suppress deterioration of coverage of an internal electrode, and can suppress deterioration of a dielectric breakdown voltage.SOLUTION: In a multilayer ceramic capacitor 10, a conductive paste for internal electrodes 13a and 13b, comprises: a metal powder; a ceramic powder; and an organic vehicle. The ceramic powder contains: a first ceramic powder of which a mean particle diameter by a BET method conversion is 3 nm or more and 25 nm or less; and a second ceramic powder of which the mean particle diameter by the BET method conversion is 40 nm or more and is less than a thickness of an internal electrode after burning. A rate of one held by a front surface of a metal powder from the first ceramic powder, is 50% or more, and a rate of the second ceramic powder held by the front surface of the metal powder is less than 20%. A rate of a total weight of the first ceramic powder and the second ceramic powder for the weight of the metal powder is 4% or more and 25% or less.SELECTED DRAWING: Figure 2

Description

The present invention is a laminate including a conductive paste for an internal electrode, a ceramic electronic component having an internal electrode formed by using the conductive paste for the internal electrode, and an internal electrode formed by using the conductive paste for the internal electrode. Regarding ceramic capacitors.

Ceramic electronic components with internal electrodes, such as multilayer ceramic capacitors, are known. In such ceramic electronic components, the internal electrodes can be formed using a conductive paste.

During firing for manufacturing ceramic electronic components, structural defects may occur due to differences in shrinkage behavior between the internal electrodes and the dielectric ceramic layer. In order to suppress the occurrence of such structural defects, a method is known in which the same ceramic powder as the ceramic powder contained in the dielectric ceramic layer is added as a co-material to the conductive paste for forming the internal electrode. ..

Patent Document 1 describes electrode ink for forming an internal electrode of a multilayer ceramic capacitor. This electrode ink contains two types of ceramic particles: ceramic particles having a particle size 1.5 to 3.0 times that of the ceramic particles contained in the dielectric ceramic layer, and ceramic particles having the same particle size. Included as material.

Patent Document 2 includes three types of co-materials having an average particle size of a, b, and c, and the average particle size b is preferably 0.05 μm to 0.4 μm, and the relationship between a, b, and c. A conductive paste in which a / b = 0.8 or more and 1.2 or less and satisfies the relationship of a and b <c is described.

Patent Document 3 describes conductivity for internal electrodes including a ceramic powder having an average particle size of 0.2 μm to 0.4 μm and a ceramic powder having an average particle size of 0.6 μm to 0.8 μm as a common material. The paste is listed.

Patent Document 4 describes a conductive paste for an internal electrode containing ceramic particles having a particle size of 10 nm and ceramic particles having a particle size of 20 nm as co-materials.

Patent Document 5 describes a laminated ceramic electronic component in which cracks and delamination are unlikely to occur inside the laminated body. The internal electrode of the laminated ceramic electronic component has substantially the same thickness as the first ceramic particle having an average particle size equal to or less than the average particle size of the conductor particles contained in the internal electrode as a common material. Includes a second ceramic particle having a certain average particle size.

JP-A-2007-214444 Japanese Unexamined Patent Publication No. 2011-150982 Japanese Unexamined Patent Publication No. 2005-267858 Korean Registered Patent No. 10-1275446 Japanese Unexamined Patent Publication No. 2000-277369

The electrode inks and conductive pastes described in Patent Documents 1 to 3 all contain a co-material having a relatively large particle size for the purpose of suppressing structural defects. In such a configuration, since the number of particles of the common material is small, it is difficult to increase the coverage and thin the internal electrode. When the amount of the co-material added is increased, the amount of the co-material discharged from the internal electrode to the dielectric ceramic layer increases, resulting in a decrease in electrical characteristics and a decrease in coverage of the internal electrode.

In particular, in the electrode ink described in Patent Document 1 and the conductive paste for internal electrodes described in Patent Document 3, the ceramic powder which is a common material is compared with the particle size of the metal powder and the thickness of the dielectric ceramic layer. Due to the large particle size, the coverage of the internal electrodes is greatly reduced. Further, since the conductive paste described in Patent Document 2 has a small difference in particle size of the common material, the effect of suppressing structural defects of ceramic electronic components is small.

The conductive paste for an internal electrode described in Patent Document 4 contains fine ceramic particles having a particle size of 10 nm and a particle size of 20 nm as a common material. When ceramic particles having a particle size of 30 nm or less are included as a common material, residual internal stress or structural defects due to the difference in thermal shrinkage behavior between the internal electrode of the ceramic electronic component and the ceramic layer occur, and the breakdown voltage (hereinafter referred to as the breakdown voltage) , Also called BDV) may decrease. This is because the co-material is likely to be discharged from the internal electrode to the dielectric layer during firing, and as a result, the internal electrode is likely to shrink at a temperature of 800 ° C. or higher.

In the laminated ceramic electronic component described in Patent Document 5, the coverage of the internal electrode is lowered because the second ceramic particles contained as the co-material are too large.

The present invention solves the above-mentioned problems, and is a conductive paste for an internal electrode capable of suppressing a decrease in coverage of an internal electrode and suppressing a decrease in an insulation breakdown voltage, such a conductive paste for an internal electrode. It is an object of the present invention to provide a ceramic electronic component and a monolithic ceramic capacitor having an internal electrode formed by using a sex paste.

The conductive paste for internal electrodes of the present invention
With metal powder
With ceramic powder
With organic vehicles
With
The ceramic powder is a first ceramic powder having an average particle size of 3 nm or more and 25 nm or less in terms of the BET method, and a first ceramic powder having an average particle size of 40 nm or more in terms of the BET method and not more than the thickness of the internal electrode after firing. Contains 2 ceramic powders
The proportion of the first ceramic powder supported on the surface of the metal powder is 50% or more, and the proportion of the second ceramic powder supported on the surface of the metal powder is 50% or more. Less than 20%
The ratio of the total weight of the first ceramic powder and the second ceramic powder to the weight of the metal powder is 4% or more and 25% or less.

When the total weight of the first ceramic powder and the second ceramic powder is 10 parts by weight, the weight of the first ceramic powder may be 5 parts by weight or more and 9 parts by weight or less.

The average particle size of the metal powder determined by SEM observation may be 40 nm or more and 300 nm or less.

The second ceramic powder has an average particle size obtained by the BET method, which is less than half the particle size of the metal powder and less than half the thickness of the internal electrode after firing, and an average particle size obtained by the BET method. It may contain a ceramic powder having a particle size equal to or more than half the thickness of the internal electrode after firing and equal to or less than the thickness of the internal electrode after firing.

The metal powder may be at least one of Ni powder and Cu powder.

The main component of the first ceramic powder and the second ceramic powder may be at least one selected from the group consisting of BaTiO ₃ , BaZrO ₃ , CaZrO ₃ , and SrZrO ₃ .

The ceramic electronic component of the present invention is characterized by including an internal electrode formed by using the above-mentioned conductive paste for an internal electrode.

Further, the multilayer ceramic capacitor of the present invention is characterized by including an internal electrode formed by using the above-mentioned conductive paste for an internal electrode.

When a ceramic electronic component or a multilayer ceramic capacitor is manufactured using the conductive paste for an internal electrode of the present invention, it is possible to suppress a decrease in coverage of the internal electrode and a decrease in an insulation breakdown voltage.

It is a perspective view of the multilayer ceramic capacitor including the internal electrode formed by using the conductive paste for an internal electrode. It is sectional drawing along the line II-II of the multilayer ceramic capacitor shown in FIG. It is sectional drawing along the line III-III of the multilayer ceramic capacitor shown in FIG.

Hereinafter, embodiments of the present invention will be shown, and the features of the present invention will be specifically described.

The conductive paste for an internal electrode of the present invention satisfies the following requirements (hereinafter referred to as the requirements of the present invention). That is, the conductive paste for internal electrodes of the present invention includes a metal powder, a ceramic powder, and an organic vehicle, and the ceramic powder is a first ceramic powder having an average particle size of 3 nm or more and 25 nm or less in terms of the BET method. And a second ceramic powder having an average particle size of 40 nm or more in terms of the BET method and not more than the thickness of the internal electrode after firing, and is supported on the surface of the metal powder among the first ceramic powders. The proportion of the powder is 50% or more, and the proportion of the second ceramic powder supported on the surface of the metal powder is less than 20%, and the ratio of the first ceramic powder and the second ceramic powder to the weight of the metal powder is less than 20%. The ratio of the total weight of the ceramic powders of 2 is 4% or more and 25% or less.

The conductive paste for an internal electrode of the present invention can be used for producing an internal electrode of a ceramic electronic component provided with an internal electrode. Ceramic electronic components are, for example, multilayer ceramic capacitors. In the following description, an example in which the conductive paste for an internal electrode of the present invention is used for manufacturing a multilayer ceramic capacitor will be described. However, the ceramic electronic component is not limited to the monolithic ceramic capacitor.

As described above, the conductive paste for an internal electrode of the present invention contains a first ceramic powder having a small particle size having an average particle size of 3 nm or more and 25 nm or less. The small particle size ceramic powder can penetrate between the metal particles to suppress the sintering of the metal particles and improve the coverage of the internal electrodes. In particular, in the conductive paste for internal electrodes of the present invention, the coverage of the internal electrodes can be further improved by setting the proportion of the first ceramic powder supported on the surface of the metal powder to 50% or more. Can be done. The coverage of the internal electrode is the coverage of the internal electrode with respect to the dielectric ceramic layer.

As described above, the conductive paste for an internal electrode of the present invention contains a second ceramic powder having an average particle size of 40 nm or more and not more than the thickness of the internal electrode after firing. Since 80% or more of the second ceramic powder is not supported by the metal powder and exists in the gaps of the metal particle-filled film, it is difficult for the second ceramic powder to be discharged from the internal electrode to the dielectric ceramic layer. Further, in the process of densification and grain growth of metal particles in the degreasing firing of a multilayer ceramic capacitor, the second ceramic powder can be effectively pinned to multiple points of the metal particles having a triple point or more, and the internal electrode shrinks. In particular, it is possible to suppress the shrinkage of the internal electrode during firing at 800 ° C. or higher. As a result, it is possible to suppress the occurrence of structural defects in the multilayer ceramic capacitor and the decrease in the dielectric breakdown voltage.

Further, since the second ceramic powder having a large particle size can form a through column connecting the dielectric ceramic layers after firing, it is possible to suppress structural defects due to electric strain when a high rated voltage is applied. it can. The structural defect due to the electric strain is, for example, peeling at the interface between the dielectric ceramic layer and the internal electrode. However, when the average particle size of the second ceramic powder is larger than the thickness of the internal electrode after firing, the shrinkage of the laminate in the stacking direction is hindered during firing, the thickness of the internal electrode is increased, and the coverage of the internal electrode is lowered. In addition, the insulation breakdown voltage drops.

The conductive paste for an internal electrode of the present invention contains a first ceramic powder having a small particle size and a second ceramic powder having a large particle size to improve the coverage of the produced internal electrode and structural defects. And the decrease in insulation breakdown voltage can be suppressed.

(Example 1)
<Preparation of conductive paste for internal electrodes>
Here, for comparison, a conductive paste for an internal electrode containing one type of ceramic powder and a conductive paste for an internal electrode containing two types of ceramic powder were prepared. As the metal powder contained in the conductive paste for the internal electrode, Ni powder was used.

A conductive paste for an internal electrode containing one type of ceramic powder was prepared by the following method. That is, 40 parts by weight of Ni powder having an SEM diameter of 200 nm, 4 parts by weight of a ceramic powder (co-material A) containing BaTiO ₃ as a main component with a BET diameter of 3 nm or more and 50 nm, and a weight average molecular weight of 23,000 and a number average. Prepare 2 parts by weight of a polycarboxylic acid-based dispersant having a molecular weight of 11,000 and 54 parts by weight of an organic vehicle composed of ethyl cellulose resin and dihydroterpineol acetate, and mix them and disperse them in a roll to conduct conductivity for internal electrodes. A sex paste was prepared.

In addition, "having BaTiO ₃ as a main component" means that at least half or more of the components are Badio ₃ . The SEM diameter of the Ni powder is the average particle size of the Ni powder obtained by SEM observation. The BET diameter of the ceramic powder is the average particle size calculated by the BET method, that is, the average particle size calculated from the specific surface area obtained by using the BET method.

Further, 40 parts by weight of Ni powder having an SEM diameter of 200 nm, 4 parts by weight of a ceramic powder (co-material B) containing BaTiO ₃ as a main component having a BET diameter of 20 nm or more and 800 nm or less, and a weight average molecular weight of 23,000 and a number. By preparing 1.5 parts by weight of a polycarboxylic acid-based dispersant having an average molecular weight of 11,000 and 54 parts by weight of an organic vehicle composed of an ethyl cellulose resin and dihydroterpineol acetate, and mixing them and dispersing them in a roll. A conductive paste for internal electrodes was prepared.

A conductive paste for an internal electrode containing two types of ceramic powder was prepared by the following method. First, 40 parts by weight of Ni powder having an SEM diameter of 200 nm, 2 parts by weight of a ceramic powder (common material A) containing BaTiO ₃ as a main component with a BET diameter of 3 nm or more and 50 nm or less, and a weight average molecular weight of 23,000 and a number. By preparing 1.5 parts by weight of a polycarboxylic acid-based dispersant having an average molecular weight of 11,000 and 40 parts by weight of an organic vehicle composed of an ethyl cellulose resin and dihydroterpineol acetate, and mixing them and dispersing them in a roll. An intermediate conductive paste was prepared.

Subsequently, 2 parts by weight of a ceramic powder (common material B) containing BaTIO ₃ as a main component having a BET diameter of 20 nm or more and 800 nm or less, and a monocarboxylic acid-based dispersant having a weight average molecular weight of 6,000 and a number average molecular weight of 6,000. A conductive paste for an internal electrode was prepared by mixing 5 parts by weight, 14 parts by weight of an organic vehicle composed of ethyl cellulose resin and dihydroterpineol acetate, adding it to the above intermediate conductive paste, and then dispersing it in a roll.

<Manufacturing of multilayer ceramic capacitors>
A monolithic ceramic capacitor was produced by the following method. First, a ceramic material containing BaTiO ₃ having a BET diameter of 250 nm as a main component and an organic binder, an organic solvent, a plasticizer and a dispersant were mixed at a predetermined ratio and wet-dispersed by roll dispersion to obtain a ceramic slurry. ..

Subsequently, the ceramic slurry was molded on the PET film by the doctor blade method to obtain a ceramic green sheet. The thickness of the ceramic slurry was adjusted so that the thickness after drying was 2.5 μm.

Subsequently, the conductive paste for the internal electrode is printed on the ceramic green sheet in a pattern such that the plane size of the chip-shaped laminate obtained later after cutting and firing is 3.2 mm × 1.6 mm. , A conductive coating film that later became an internal electrode was formed. The conductive paste for the internal electrode was printed by a screen printing machine so that the average thickness after drying by XRF measurement was 0.4 μm.

Subsequently, the ceramic green sheet on which the conductive coating film was formed was peeled off from the PET film, and 200 peeled ceramic green sheets were laminated and placed in a predetermined mold. However, a predetermined number of ceramic green sheets on which no conductive coating film was formed were arranged on both outer sides in the stacking direction. Then, the whole was pressed and cut into a predetermined size to obtain a raw chip-like laminate.

Subsequently, the obtained raw laminate was degreased by heating it in nitrogen at a temperature of 280 ° C. for 10 hours, and then the oxygen partial pressure was 10 ^-16 MPa or more and 10 ^-14 MPa or less. _In a mixed atmosphere of ₂ , H ₂ , and H ₂ O, hold at 800 ° C. for 3 hours, and further mix N ₂ , H ₂ , and H ₂ O having an oxygen partial pressure of 10 ^-9 MPa or more and 10 ^-8 MPa or less. A sintered body was obtained by firing at 1210 ° C. for 2 hours in an atmosphere. In this sintered body, the thickness of the internal electrode at 76% coverage was 0.6 μm.

A multilayer ceramic capacitor can be obtained by forming external electrodes at both ends of the sintered body, more specifically, at both ends where the internal electrodes are exposed.

FIG. 1 is a perspective view of the multilayer ceramic capacitor 10 manufactured by the above method. FIG. 2 is a cross-sectional view of the multilayer ceramic capacitor 10 shown in FIG. 1 along the line II-II. FIG. 3 is a cross-sectional view of the multilayer ceramic capacitor 10 shown in FIG. 1 along lines III-III.

As shown in FIGS. 1 to 3, the multilayer ceramic capacitor 10 is a ceramic electronic component having a rectangular parallelepiped shape as a whole, and has a ceramic element 11 and a first external electrode 14a and a second external electrode 14b. are doing.

Here, the direction in which the first external electrode 14a and the second external electrode 14b face each other is defined as the length direction L of the laminated ceramic capacitor 10, and the dielectric ceramic layer 12 and the internal electrodes 13a and 13b described later are defined as each other. The stacking direction is defined as the stacking direction T, and the direction orthogonal to both the length direction L and the stacking direction T is defined as the width direction W.

As shown in FIGS. 2 and 3, the ceramic element 11 includes a plurality of laminated dielectric ceramic layers 12 and a plurality of internal electrodes 13a and 13b. The internal electrodes 13a and 13b include a first internal electrode 13a and a second internal electrode 13b. More specifically, the ceramic element 11 has a structure in which a plurality of first internal electrodes 13a and second internal electrodes 13b are alternately laminated via the dielectric ceramic layer 12 in the stacking direction T. The thickness of the first internal electrode 13a and the second internal electrode 13b is preferably 0.3 μm or more and 1.0 μm or less.

As shown in FIG. 1, the first external electrode 14a and the second external electrode 14b are arranged so as to face each other. The first external electrode 14a is electrically connected to the first internal electrode 13a, and the second external electrode 14b is electrically connected to the second internal electrode 13b.

<Coverage judgment and BDV judgment>
Of the prepared sintered bodies, any 10 pieces were peeled off at the interface between the internal electrode and the dielectric ceramic layer, and the ratio of the metal portion on the peeled surface was calculated as the coverage of the internal electrode. Here, when the coverage is less than 70%, it indicates that it is NG, when it is 70% or more and less than 75%, it indicates that it is OK, and when it is 75% or more. It was judged as "◎" indicating that it is very good.

Further, after baking copper electrodes as external electrodes on both ends of the sintered body, a DC-BDV test for obtaining a dielectric breakdown voltage was performed. In this DC-BDV test, the boosting speed was 100 V / sec, the detection current was 83 mA, and the DC voltage at which the multilayer ceramic capacitor was short-circuited was determined as the breakdown voltage. Here, "x" indicating NG when the number of arbitrary 30 multilayer ceramic capacitors having a breakdown voltage of 100 V or less is 4 or more, and OK when 1 or more and 3 or less are present. It was determined that "○" indicates that the value is, and "◎" indicates that the number is very good.

The results obtained are shown in Table 1.

In Table 1, for each sample of sample numbers 1 to 38, the SEM diameter of Ni powder, the BET diameter of co-material A, the BET diameter of co-material B, the addition weight ratio of co-material A and co-material B, and the addition weight of nickel. The ratio of the total weight added to the common material A and the common material B, the coverage of the internal electrode, the number of NG of BDV, the coverage judgment, and the BDV judgment are shown. The number of NGs in BDV is the number of multilayer ceramic capacitors having a breakdown voltage of 100 V or less in the DC-BDV test.

In the samples of sample numbers 12 to 38 using the ceramic powders of the common material A and the common material B, the ratio of the ceramic powder of the common material A supported on the surface of the metal powder is 50% or more, and both It was confirmed that the proportion of the ceramic powder of the material B supported on the surface of the metal powder was less than 20%.

In Table 1, the samples with * in the sample number are the samples that do not meet the above-mentioned requirements of the present invention, and the samples without the * in the sample number satisfy the requirements of the present invention. It is a sample.

In the sample satisfying the requirements of the present invention, the ceramic powder of the common material A is the first ceramic powder, and the ceramic powder of the common material B is the second ceramic powder. The same applies to Tables 2 to 7 described later.

As shown in Table 1, for the samples of sample numbers 1 to 11 produced by using the conductive paste for internal electrodes containing one type of ceramic powder as a co-material and not satisfying the requirements of the present invention, coverage determination and At least one of the BDV judgments was "x".

In addition, sample numbers 12 to 14, 23, 28, which are produced by using a conductive paste for an internal electrode, which contains two types of ceramic powders as co-materials but whose BET diameter of the ceramic powder does not meet the requirements of the present invention. For the samples 33 to 38, at least one of the coverage judgment and the BDV judgment was “x”. The thickness of the internal electrode after firing is 600 nm.

That is, in the sample produced by using the conductive paste for the internal electrode which does not satisfy the requirements of the present invention, at least one of the defects of the decrease in the coverage of the internal electrode and the decrease in the insulation breakdown voltage occurred.

In the sample produced by using the conductive paste for the internal electrode having a BET diameter of 800 nm of the ceramic powder which is the common material B, the thickness of the large particle size ceramic powder is equal to or larger than the physical thickness of the internal electrode after firing. is there. For this reason, the large-grained ceramic powder hinders shrinkage in the stacking direction during firing, and the thickness of the internal electrodes in the stacking direction becomes thicker, resulting in reduced coverage and beating of the internal electrodes, resulting in an insulation breakdown voltage. Is considered to decrease.

On the other hand, in the samples of sample numbers 15 to 22, 24 to 27, and 29 to 32 produced by using the conductive paste for the internal electrode satisfying the requirements of the present invention, the coverage judgment and the BDV judgment were " None of them were judged as "x", and they were either "○" or "◎".

That is, the monolithic ceramic capacitor manufactured by using the conductive paste for an internal electrode satisfying the requirements of the present invention has high internal electrode coverage and a high breakdown voltage. In particular, using a conductive paste for an internal electrode that meets the requirements of the present invention, a large laminated ceramic having a length L dimension of 1.6 mm or more and a width direction W and a lamination direction T of 0.8 mm or more. When a capacitor or a multilayer ceramic capacitor with a high rated voltage is manufactured, the effect of increasing the coverage of the internal electrode and suppressing the decrease in the insulation breakdown voltage is great.

(Example 2)
For the purpose of confirming the effect of changing the ratio of the total weight of the ceramic powder of the common material A and the ceramic powder of the common material B to the weight of the metal powder, the samples of sample numbers 41 to 50 in Table 2 were prepared. Further, in each of the samples of sample numbers 41 to 50, the ratio of the ceramic powder of the common material A supported on the surface of the metal powder is 50% or more, and the metal powder of the ceramic powder of the common material B is supported. It was confirmed that the proportion of those supported on the surface of the ceramic was less than 20%.

In Table 2, the samples marked with * in the sample number are the samples that do not meet the above-mentioned requirements of the present invention, and the samples not marked with * in the sample number meet the requirements of the present invention. It is a sample.

The conductive paste for the internal electrode used to prepare each sample was prepared by the following method. First, 40 parts by weight of Ni powder having an SEM diameter of 200 nm, a predetermined weight part of 0.4 parts by weight or more and 8 parts by weight or less of a ceramic powder (co-material A) containing Badio ₃ as a main component having a BET diameter of 7 nm or 25 nm, and , 35 parts by weight or more and 45 parts by weight or less of an organic vehicle composed of 1.5 parts by weight of a polycarboxylic acid-based dispersant having a weight average molecular weight of 23,000 and a number average molecular weight of 11,000, an ethyl cellulose resin and dihydroterpineol acetate. A predetermined weight portion of each was prepared, and they were mixed and rolled to be dispersed to prepare an intermediate conductive paste.

Subsequently, a predetermined weight part of 0.4 parts by weight or more and 8 parts by weight or less of the second ceramic powder (common material B) containing BaTiO ₃ as a main component having a BET diameter of 40 nm or 500 nm, and a weight average molecular weight of 6,000 Prepare 0.5 parts by weight of a monocarboxylic acid-based dispersant having a number average molecular weight of 6,000 and an organic vehicle composed of ethyl cellulose resin and dihydroterpineol acetate in a predetermined weight portion of 7 parts by weight or more and 12.2 parts by weight or less, and prepare them. A conductive paste for an internal electrode was prepared by mixing and adding to the above-mentioned intermediate conductive paste and then dispersing in a roll.

After that, a sintered body and a multilayer ceramic capacitor in which external electrodes were formed at both ends of the sintered body were manufactured by the same manufacturing method as that described in Example 1. Further, with respect to the produced sintered body and the multilayer ceramic capacitor, the coverage determination and the BDV determination of the internal electrodes were performed by the same method as described in Example 1.

In the samples of sample numbers 41 to 45 in Table 2, the BET diameter of the ceramic powder of the common material A is 7 nm, the BET diameter of the ceramic powder of the common material B is 40 nm, the weight of the ceramic powder of the common material A and the ceramic of the common material B. The ratio to the weight of the powder is 5: 5.

In the samples of sample numbers 46 to 50 in Table 2, the BET diameter of the ceramic powder of the common material A is 25 nm, the BET diameter of the ceramic powder of the common material B is 500 nm, and the weight of the ceramic powder of the common material A and the common material B. The ratio of the ceramic powder to the weight of the ceramic powder is 5: 5.

As shown in Table 2, the ratio of the total weight of the ceramic powder of the common material A and the ceramic powder of the common material B to the weight of the Ni powder is 4% or more and 25% or less, and the sample number 42 satisfying the requirements of the present invention. The samples of ~ 44 and 47 to 49 were not judged as “x” in each of the coverage judgment and the BDV judgment, and were “◯” or “⊚”.

On the other hand, the ratio of the total weight of the ceramic powder of the co-material A and the ceramic powder of the co-material B to the weight of the Ni powder is less than 4% or more than 25%, and the requirements of the present invention are not satisfied. For the samples 46 and 50, at least one of the coverage judgment and the BDV judgment was "x".

As described above, in order to suppress the decrease in the coverage of the internal electrodes and the decrease in the breakdown voltage, the ratio of the total weight of the first ceramic powder and the second ceramic powder to the weight of the metal powder is 4% or more and 25%. It needs to be:

(Example 3)
Of the ceramic powder of the common material A, the ratio of those supported on the surface of the metal powder is 50% or more, and the ratio of the ceramic powder of the common material B supported on the surface of the metal powder is 50% or more. For the purpose of confirming the effect of less than 20%, the samples of sample numbers 51 to 58 in Table 3 were prepared.

In all the samples in Table 3, the proportion of the ceramic powder of the common material B supported on the surface of the metal powder is less than 20%. Further, in Table 3, in the samples of sample numbers 55 to 58 in which * is attached to the sample number, the proportion of the ceramic powder of the common material A supported on the surface of the metal powder is less than 50%. It is a sample that does not satisfy the requirements of the present invention. On the other hand, the samples not marked with * in the sample number are the samples in which the proportion of the ceramic powder of the common material A supported on the surface of the metal powder is 50% or more and satisfy the requirements of the present invention. is there.

The samples of sample numbers 51 to 54 are the same as the samples of sample numbers 17, 21, 26, and 31 in Table 1.

A conductive paste for an internal electrode in which 50% or more of the ceramic powder of the common material A is supported on the metal powder was produced by the following method.

First, 40 parts by weight of Ni powder having an SEM diameter of 200 nm, 2 parts by weight of a ceramic powder (co-material A) containing BaTiO ₃ as a main component with a BET diameter of 15 nm, and a weight average molecular weight of 23,000 and a number average molecular weight of 1. Prepare 1.5 parts by weight of each of 1,000 polycarboxylic acid-based dispersants and 40 parts by weight of an organic vehicle composed of ethyl cellulose resin and dihydroterpineol acetate, mix them and disperse them in a roll to form an intermediate conductive paste. Was produced.

Subsequently, 2 parts by weight of a ceramic powder (common material B) containing BaTIO ₃ as a main component having a BET diameter of 40 nm or more and 500 nm or less, and a monocarboxylic acid-based dispersant having a weight average molecular weight of 6,000 and a number average molecular weight of 6,000. A conductive paste for an internal electrode was prepared by mixing 5 parts by weight, 14 parts by weight of an organic vehicle composed of ethyl cellulose resin and dihydroterpineol acetate, adding it to the above intermediate conductive paste, and then dispersing it in a roll.

Observing the SEM image of the dry coating surface of the prepared conductive paste for internal electrodes, 50 or more of the 100 particles of the ceramic powder of the common material A, that is, the first cellac powder were supported on the surface of the Ni particles. It was confirmed that 16 or more of the 20 particles of the common material B ceramic powder, that is, the second ceramic powder, were not supported on the surface of the Ni particles. That is, the proportion of the first ceramic powder supported on the surface of the Ni powder is 50% or more, and the proportion of the second ceramic powder supported on the Ni powder is less than 20%. is there.

A conductive paste for an internal electrode in which 50% or more of the ceramic powder of the common material A was not supported on the metal powder was prepared by the following method.

First, 40 parts by weight of Ni powder having an SEM diameter of 200 nm, 2 parts by weight of a ceramic powder (co-material A) containing BaTiO ₃ as a main component with a BET diameter of 15 nm, and a weight average molecular weight of 6,000 and a number average molecular weight of 6,000. An intermediate conductive paste was prepared by preparing 1.5 parts by weight of a monocarboxylic acid-based dispersant, 40 parts by weight of an organic vehicle composed of an ethyl cellulose resin and dihydroterpineol acetate, mixing them and dispersing them in a roll. ..

Subsequently, 2 parts by weight of a ceramic powder (common material B) containing BaTIO ₃ as a main component having a BET diameter of 40 nm or more and 500 nm or less, and a monocarboxylic acid-based dispersant having a weight average molecular weight of 6,000 and a number average molecular weight of 6,000. A conductive paste for an internal electrode was prepared by mixing 5 parts by weight, 14 parts by weight of an organic vehicle composed of ethyl cellulose resin and dihydroterpineol acetate, adding it to the above intermediate conductive paste, and then dispersing it in a roll.

Observing the SEM image of the dry coating surface of the prepared conductive paste for internal electrodes, 50 or more of the 100 particles of the cellac powder of the common material A were not supported on the surface of the Ni particles, and the common material was used. It was confirmed that 16 or more of the 20 particles of the ceramic powder of B were not supported on the surface of the Ni particles. That is, the proportion of the ceramic powder of the common material A supported by the Ni powder is less than 50%, and the proportion of the ceramic powder of the common material B supported by the Ni powder is less than 20%. is there.

After that, a sintered body and a multilayer ceramic capacitor in which external electrodes were formed at both ends of the sintered body were manufactured by the same manufacturing method as that described in Example 1. Further, with respect to the produced sintered body and the multilayer ceramic capacitor, the coverage determination and the BDV determination of the internal electrodes were performed by the same method as described in Example 1.

The ratio of the first ceramic powder supported on the surface of the Ni powder is 50% or more, and the ratio of the second ceramic powder supported on the surface of the Ni powder is less than 20%. Yes, the samples of sample numbers 51 to 54 prepared by using the conductive paste for internal electrodes satisfying the requirements of the present invention were not judged as "x" in each of the coverage judgment and the BDV judgment, and "x" was not found. It became "○" or "◎".

On the other hand, among the ceramic powders of the common material A, the proportion of those supported on the surface of the Ni powder is less than 50%, and the sample is prepared by using the conductive paste for internal electrodes which does not satisfy the requirements of the present invention. The coverage judgment of all the samples of Nos. 55 to 58 was "x".

That is, in order to suppress the decrease in the coverage of the internal electrode and the decrease in the insulation breakdown voltage, the conductive paste for the internal electrode is the first ceramic powder having a BET diameter of 3 nm or more and 25 nm or less, and the BET diameter of 40 nm or more and firing. It is not enough to include the second ceramic powder which is less than or equal to the thickness of the later internal electrode, and it is necessary that 50% or more of the first ceramic powder is supported by the metal powder.

If the second ceramic powder having a large particle size is supported on the metal powder, the first ceramic powder having a small particle size cannot be supported on the metal powder, and the metal filling rate of the electrode coating film is lowered. To do. Therefore, it is important to support the first ceramic powder having a small particle size on the metal powder.

(Example 4)
For the purpose of confirming the effect when the weight ratio of the ceramic powder of the common material A and the ceramic powder of the common material B was changed, the samples of sample numbers 61 to 75 in Table 4 were prepared. Further, in the sample using the ceramic powder of the common material A and the common material B, the ratio of the ceramic powder of the common material A supported on the surface of the metal powder is 50% or more, and the ceramic of the common material B is ceramic. It was confirmed that the proportion of the powder supported on the surface of the metal powder was less than 20%.

In Table 4, the samples marked with * in the sample number are samples that do not meet the requirements of the present invention because there is only one type of ceramic powder contained as a co-material, and the sample numbers are not marked with *. The sample is a sample that meets the requirements of the present invention.

A conductive paste for an internal electrode containing one type of ceramic powder was prepared by the following method. That is, 40 parts by weight of Ni powder having an SEM diameter of 200 nm, 4 parts by weight of a ceramic powder (co-material A) containing BaTiO ₃ as a main component with a BET diameter of 7 nm or more and 25 nm or less, and a weight average molecular weight of 23,000 and a number. Prepare 2 parts by weight of a polycarboxylic acid-based dispersant having an average molecular weight of 11,000, 54 parts by weight of an organic vehicle composed of ethyl cellulose resin and dihydroterpineol acetate, mix them, and disperse them in a roll to form an internal electrode. A conductive paste for use was prepared.

Further, 40 parts by weight of Ni powder having an SEM diameter of 200 nm, 4 parts by weight of a ceramic powder (co-material B) containing BaTiO ₃ as a main component having a BET diameter of 40 nm or more and 500 nm or less, and a weight average molecular weight of 6,000 and a number average molecular weight. Prepare 54 parts by weight of organic vehicles consisting of 2 parts by weight of 6,000 polycarboxylic acid-based dispersants, ethyl cellulose resin and dihydroterpineol acetate, mix them and disperse them in a roll to make a conductive paste for internal electrodes. Was produced.

A conductive paste for an internal electrode containing two types of ceramic powder was prepared by the following method. First, 40 parts by weight of Ni powder of SEM diameter 200 nm, predetermined weight ceramic powder (common material A) below 3.6 parts by weight or more and 1.2 parts by weight of the main component BET diameter 7nm more 25nm following BaTiO ₃ 40 parts by weight of 1.5 parts by weight of a polycarboxylic acid-based dispersant having a weight average molecular weight of 23,000 and a number average molecular weight of 11,000, and 40 parts by weight of an organic vehicle composed of ethyl cellulose resin and dihydroterpineol acetate. Then, they were mixed and rolled to be dispersed to prepare an intermediate conductive paste.

Subsequently, a predetermined weight part of 0.4 parts by weight or more and 2.8 parts by weight or less of a ceramic powder (co-material B) containing BaTiO ₃ as a main component having a BET diameter of 40 nm or more and 500 nm or less, and a weight average molecular weight of 6,000 0.5 parts by weight of a monocarboxylic acid-based dispersant having a number average molecular weight of 6,000 and 14 parts by weight of an organic vehicle composed of ethyl cellulose resin and dihydroterpineol acetate are mixed, added to the above intermediate conductive paste, and then rolled and dispersed. By doing so, a conductive paste for an internal electrode was prepared.

After that, a sintered body and a multilayer ceramic capacitor in which external electrodes were formed at both ends of the sintered body were manufactured by the same manufacturing method as that described in Example 1. Further, with respect to the produced sintered body and the multilayer ceramic capacitor, the coverage determination and the BDV determination of the internal electrodes were performed by the same method as described in Example 1.

The samples of sample numbers 62 to 64, 67 to 69, and 72 to 74 are samples prepared by using a conductive paste for an internal electrode that satisfies the requirements of the present invention. None of these samples was judged as "x" in each of the coverage judgment and the BDV judgment, and were "○" or "◎".

Of the samples of sample numbers 62 to 64, 67 to 69, 72 to 74, the samples of sample numbers 62, 63, 67, 68, 72 and 73 satisfy the requirements of the present invention and are the first of the common materials A. With a sample satisfying the requirement that the weight of the first ceramic powder is 5 parts by weight or more and 9 parts by weight or less when the total weight of the ceramic powder of the above and the second ceramic powder of the co-material B is 10 parts by weight. is there. For these samples, at least one of the coverage judgment and the BDV judgment was "⊚".

That is, the conductive paste for internal electrodes satisfying the requirements of the present invention has a weight of 5 parts by weight of the first ceramic powder when the total weight of the first ceramic powder and the second ceramic powder is 10 parts by weight. It is preferably 2 parts or more and 9 parts by weight or less. Focusing on the weight of the second ceramic powder, when the total weight of the first ceramic powder and the second ceramic powder is 10 parts by weight, the weight of the second ceramic powder is 1 part by weight or more and 5 parts by weight. The following is preferable.

(Example 5)
For the purpose of confirming the effect when the particle size of the metal powder was changed, the samples of sample numbers 81 to 85 in Table 5 were prepared. In each sample of sample numbers 81 to 85, the proportion of the ceramic powder of the common material A supported on the surface of the metal powder is 50% or more, and the surface of the metal powder of the ceramic powder of the common material B is 50% or more. It was confirmed that the proportion of those carried in the ceramic was less than 20%. All the samples of sample numbers 81 to 85 in Table 5 meet the requirements of the present invention.

The conductive paste for the internal electrode used to prepare each sample was prepared by the following method. First, 40 parts by weight of Ni powder having an SEM diameter of 40 nm or more and 500 nm or less, 2 parts by weight of a ceramic powder (co-material A) containing Badio ₃ as a main component with a BET diameter of 7 nm, and a weight average molecular weight of 23,000 and a number. By preparing 1.5 parts by weight of a polycarboxylic acid-based dispersant having an average molecular weight of 11,000 and 40 parts by weight of an organic vehicle composed of an ethyl cellulose resin and dihydroterpineol acetate, and mixing them and dispersing them in a roll. An intermediate conductive paste was prepared.

Subsequently, 2 parts by weight of a ceramic powder (common material B) containing BaTiO ₃ having a BET diameter of 60 nm as a main component, and 0.5 parts by weight of a monocarboxylic acid-based dispersant having a weight average molecular weight of 6,000 and a number average molecular weight of 6,000. 14 parts by weight of an organic vehicle composed of ethyl cellulose resin and dihydroterpineol acetate was mixed, added to the above-mentioned intermediate conductive paste, and then rolled and dispersed to prepare a conductive paste for an internal electrode.

After that, a sintered body and a multilayer ceramic capacitor in which external electrodes were formed at both ends of the sintered body were manufactured by the same manufacturing method as that described in Example 1. However, the conductive paste formed on the ceramic green sheet was printed so that the average thickness after drying by XRF measurement was 0.5 μm.

Further, with respect to the produced sintered body and the multilayer ceramic capacitor, the coverage determination and the BDV determination of the internal electrodes were performed by the same method as described in Example 1.

The samples of sample numbers 81 to 85 prepared using the conductive paste for the internal electrode satisfying the requirements of the present invention were not judged as "x" in each of the coverage judgment and the BDV judgment, and were "○". Or "◎".

Among the samples of sample numbers 81 to 85, the samples of sample numbers 81 to 84 are samples that satisfy the requirements of the present invention and have a Ni powder particle size of 40 nm or more and 300 nm or less. The coverage judgment of all these samples was "◎".

That is, among the conductive pastes for internal electrodes that satisfy the requirements of the present invention, the coverage of the internal electrodes can be further improved by setting the particle size of the metal powder to 40 nm or more and 300 nm or less. Therefore, the particle size of the metal powder is preferably 40 nm or more and 300 nm or less.

(Example 6)
For the purpose of confirming the effect when Cu powder was used instead of Ni powder as the metal powder, the samples of sample numbers 91 to 93 in Table 6 were prepared. In the sample of sample number 92, the proportion of the ceramic powder of the common material A supported on the surface of the metal powder is 50% or more, and the ceramic powder of the common material B is supported on the surface of the metal powder. It was confirmed that the proportion of ceramics was less than 20%.

In Table 6, the samples marked with * in the sample number are samples that do not meet the requirements of the present invention because one type of ceramic powder is contained as a co-material, and the sample numbers are not marked with *. The sample is a sample that meets the requirements of the present invention.

The conductive paste for the internal electrode used to prepare each sample was prepared by the following method.

A conductive paste for an internal electrode containing one type of ceramic powder was prepared by the following method. That is, 40 parts by weight of Cu powder having an SEM diameter of 300 nm, 4 parts by weight of a ceramic powder (co-material A) containing Badio ₃ as a main component having a BET diameter of 15 nm, and a weight average molecular weight of 23,000 and a number average molecular weight of 1. Prepare 54 parts by weight of organic vehicles consisting of 2 parts by weight of 11,000 polycarboxylic acid-based dispersants, ethyl cellulose resin and dihydroterpineol acetate, and mix them and disperse them in a roll to make them conductive for internal electrodes. A paste was made.

Further, 40 parts by weight of Cu powder having an SEM diameter of 300 nm, 4 parts by weight of a ceramic powder (co-material B) containing BaTiO ₃ as a main component having a BET diameter of 60 nm, and a weight average molecular weight of 6,000 and a number average molecular weight of 6,000. 54 parts by weight of an organic vehicle composed of 2 parts by weight of a polycarboxylic acid-based dispersant, an ethyl cellulose resin and dihydroterpineol acetate was prepared, and these were mixed and roll-dispersed to prepare a conductive paste for an internal electrode. ..

A conductive paste for an internal electrode containing two types of ceramic powder was prepared by the following method. First, 40 parts by weight of Cu powder having an SEM diameter of 300 nm, 2 parts by weight of a ceramic powder (co-material A) containing Badio ₃ as a main component with a BET diameter of 15 nm, and a weight average molecular weight of 23,000 and a number average molecular weight of 1. Prepare 14 parts by weight of organic vehicles consisting of 1.5 parts by weight of a 1,000 polycarboxylic acid-based dispersant, ethyl cellulose resin and dihydroterpineol acetate, mix them and disperse them in a roll to achieve intermediate conductivity. A paste was made.

Subsequently, 2 parts by weight of a ceramic powder (common material B) containing BaTiO ₃ having a BET diameter of 60 nm as a main component, and 0.5 parts by weight of a monocarboxylic acid-based dispersant having a weight average molecular weight of 6,000 and a number average molecular weight of 6,000. 14 parts by weight of an organic vehicle composed of ethyl cellulose resin and dihydroterpineol acetate was mixed, added to the above-mentioned intermediate conductive paste, and then rolled and dispersed to prepare a conductive paste for an internal electrode.

After that, a sintered body and a multilayer ceramic capacitor in which external electrodes were formed at both ends of the sintered body were manufactured by the same manufacturing method as that described in Example 1. However, the conductive paste formed on the ceramic green sheet was printed so that the average thickness after drying by XRF measurement was 0.6 μm.

Further, with respect to the produced sintered body and the multilayer ceramic capacitor, the coverage determination and the BDV determination of the internal electrodes were performed by the same method as described in Example 1.

As shown in Table 6, for the samples of sample numbers 91 and 93 produced using the conductive paste for internal electrodes containing only one type of ceramic powder as a co-material, the coverage judgment or BDV judgment is “x”. It was.

On the other hand, in the sample of sample number 92 produced by using the conductive paste for the internal electrode satisfying the requirements of the present invention, the coverage determination and the BDV determination were "◯", respectively.

That is, even when Cu powder is used instead of Ni powder as the metal powder, it is possible to manufacture a monolithic ceramic capacitor having high coverage of internal electrodes and high breakdown voltage. Therefore, the metal powder contained in the conductive paste for the internal electrode may be at least one of Ni powder and Cu powder.

(Example 7)
As the main component of the ceramic powder, in place of _{BaTiO 3, BaZrO 3, CaZrO 3} , or, for the purpose of confirming the effect of using SrZrO _3, to prepare a sample of the sample No. 101-109 in Table 7. Further, among the samples of sample numbers 101 to 109, in the samples using the ceramic powders of the common material A and the common material B, the ratio of the ceramic powders of the common material A supported on the surface of the metal powder is It was confirmed that the percentage was 50% or more, and the proportion of the ceramic powder of the common material B supported on the surface of the metal powder was less than 20%.

In Table 7, the samples marked with * in the sample number are samples that do not meet the requirements of the present invention because one type of ceramic powder is contained as a co-material, and the sample numbers are not marked with *. The sample is a sample that meets the requirements of the present invention.

A conductive paste for an internal electrode containing one type of ceramic powder was prepared by the following method. That is, 40 parts by weight of Ni powder having an SEM diameter of 200 nm, 4 parts by weight of a ceramic powder (co-material A) containing BaZrO ₃ , CaZrO ₃ or SrZrO ₃ as a main component, and a weight average molecular weight of 6 Prepare 54 parts by weight of organic vehicles consisting of 2 parts by weight of a monocarboxylic acid-based dispersant having a thousand and several average molecular weights of 6,000, ethyl cellulose resin and dihydroterpineol acetate, and mix them and disperse them in a roll. A conductive paste for electrodes was prepared.

The phrase "mainly composed of BaZrO ₃ , CaZrO ₃ , or SrZrO ₃ " means that at least half or more of the components are BaZrO ₃ , CaZrO ₃ , or SrZrO ₃ .

Further, 40 parts by weight of Ni powder having an SEM diameter of 200 nm, 4 parts by weight of a ceramic powder (co-material B) containing BaZrO ₃ , CaZrO ₃ or SrZrO ₃ as a main component, and a weight average molecular weight of 6 are used. Prepare 54 parts by weight of an organic vehicle composed of 2 parts by weight of a polycarboxylic acid-based dispersant having a thousand and a number average molecular weight of 6,000, an ethyl cellulose resin, and dihydroterpineol acetate, and mix them and disperse them in a roll. A conductive paste for electrodes was prepared.

A conductive paste for an internal electrode containing two types of ceramic powder was prepared by the following method. First, 40 parts by weight of Ni powder having an SEM diameter of 200 nm, 2 parts by weight of a ceramic powder (co-material A) containing BaZrO ₃ , CaZrO ₃ or SrZrO ₃ as a main component, and a weight average molecular weight of 2 Prepare 1.5 parts by weight of a polycarboxylic acid-based dispersant having 13,000 and a number average molecular weight of 11,000, and 40 parts by weight of an organic vehicle composed of ethyl cellulose resin and dihydroterpineol acetate, mix them, and roll them. By dispersing, an intermediate conductive paste was prepared.

Subsequently, 2 parts by weight of a ceramic powder (co-material B) containing BaZrO ₃ , CaZrO ₃ , or SrZrO ₃ as a main component having a BET diameter of 80 nm, and a monocarboxylic acid having a weight average molecular weight of 6,000 and a number average molecular weight of 6,000. By mixing 0.5 parts by weight of the system dispersant, 14 parts by weight of an organic vehicle composed of ethyl cellulose resin and dihydroterpineol acetate, adding it to the above intermediate conductive paste, and then rolling-dispersing it, the conductivity for the internal electrode is made. A paste was made. However, the main component of the ceramic powder of the common material A and the main component of the ceramic powder of the common material B contained in one conductive paste for the internal electrode are the same.

After that, a sintered body and a multilayer ceramic capacitor in which external electrodes were formed at both ends of the sintered body were manufactured by the same manufacturing method as that described in Example 1. Further, with respect to the produced sintered body and the multilayer ceramic capacitor, the coverage determination and the BDV determination of the internal electrodes were performed by the same method as described in Example 1.

As shown in Table 7, the coverage of the samples of sample numbers 101, 103, 104, 106, 107, and 109 produced using the conductive paste for internal electrodes containing only one type of ceramic powder as a co-material. The judgment or BDV judgment was "x".

On the other hand, in the samples of sample numbers 102, 105, and 108 produced by using the conductive paste for the internal electrode satisfying the requirements of the present invention, the coverage determination and the BDV determination were "◯", respectively.

Therefore, even when the main components of the first ceramic powder and the second ceramic powder contained in the conductive paste for the internal electrode are BaZrO ₃ , CaZrO ₃ , or SrZrO ₃ , the main components are BaTIO _3. Similarly, a monolithic ceramic capacitor having high coverage of internal electrodes and a high breakdown voltage can be manufactured.

That is, considering the results of Examples 1 to 7, if the main component of the ceramic powder is at least one selected from the group consisting of BaTiO ₃ , BaZrO ₃ , CaZrO ₃ , and SrZrO ₃ , the internal electrode It is possible to manufacture a monolithic ceramic capacitor having high coverage and high dielectric breakdown voltage.

The present invention is not limited to the above embodiment, and various applications and modifications can be added within the scope of the present invention. For example, the characteristic configurations described in Examples 1 to 7 can be combined as appropriate.

Two or more kinds of ceramic powders may be used as the second ceramic powder. For example, the second ceramic powder is a ceramic powder whose average particle size in terms of the BET method is less than half the particle size of the metal powder and less than half the thickness of the internal electrode after firing, and the average particle size in terms of the BET method. It may contain ceramic powder having a diameter equal to or more than half the thickness of the internal electrode after firing and equal to or less than the thickness of the internal electrode after firing. In that case, one of the two types of ceramic powder, which is the second ceramic powder, functions as a ceramic powder for suppressing discharge from the internal electrode to the dielectric layer during firing, and the other is dielectric. Since it acts as a through column connecting the layers of the body ceramic and functions as a ceramic powder for suppressing structural defects, it is possible to manufacture a laminated ceramic electronic component having more excellent characteristics.

10 Multilayer Ceramic Capacitor 11 Ceramic Element 12 Dielectric Layer 13a First Internal Electrode 13b Second Internal Electrode 14a First External Electrode 14b Second External Electrode

Claims (8)

With metal powder
With ceramic powder
With organic vehicles
With
The ceramic powder is a first ceramic powder having an average particle size of 3 nm or more and 25 nm or less in terms of the BET method, and a first ceramic powder having an average particle size of 40 nm or more in terms of the BET method and not more than the thickness of the internal electrode after firing. Contains 2 ceramic powders
The proportion of the first ceramic powder supported on the surface of the metal powder is 50% or more, and the proportion of the second ceramic powder supported on the surface of the metal powder is 50% or more. Less than 20%
A conductive paste for an internal electrode, wherein the ratio of the total weight of the first ceramic powder and the second ceramic powder to the weight of the metal powder is 4% or more and 25% or less. When the total weight of the first ceramic powder and the second ceramic powder is 10 parts by weight, the weight of the first ceramic powder is 5 parts by weight or more and 9 parts by weight or less. The conductive paste for an internal electrode according to claim 1. The conductive paste for an internal electrode according to claim 1 or 2, wherein the average particle size of the metal powder determined by SEM observation is 40 nm or more and 300 nm or less. The second ceramic powder has an average particle size obtained by the BET method, which is less than half the particle size of the metal powder and less than half the thickness of the internal electrode after firing, and an average particle size obtained by the BET method. The interior according to any one of claims 1 to 3, wherein the ceramic powder having a particle size of at least half the thickness of the internal electrode after firing and at least the thickness of the internal electrode after firing is included. Conductive paste for electrodes. The conductive paste for an internal electrode according to any one of claims 1 to 4, wherein the metal powder is at least one of Ni powder and Cu powder. 1. The main component of the first ceramic powder and the second ceramic powder is at least one selected from the group consisting of BaTiO ₃ , BaZrO ₃ , CaZrO ₃ , and SrZrO _3. 5. The conductive paste for an internal electrode according to any one of 5. A ceramic electronic component comprising an internal electrode formed by using the conductive paste for an internal electrode according to any one of claims 1 to 6. A monolithic ceramic capacitor comprising an internal electrode formed by using the conductive paste for an internal electrode according to any one of claims 1 to 6.

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