JP6447903B2 - Method for manufacturing conductive paste for multilayer ceramic electronic component, method for manufacturing multilayer ceramic electronic component using this conductive paste, and method for manufacturing multilayer ceramic capacitor by this method - Google Patents

Description

  The present invention relates to a conductive paste that secures continuity of internal electrodes in a multilayer ceramic electronic component, suppresses variation in capacitance, and reduces its dielectric loss, and also relates to a multilayer ceramic capacitor using this conductive pace. It is.

In general, a chip-type multilayer ceramic capacitor has a cubic shape and includes external electrodes for mounting on both side surfaces in the longitudinal direction. The cross-sectional structure of the multilayer ceramic capacitor is such that dielectric layers and internal electrode layers are laminated in multiple layers. The internal electrodes are alternately connected to only one external electrode for each layer.
In recent years, electronic devices such as mobile phones and portable terminals, lighter and thinner devices, and higher frequency digital devices, it is desirable to reduce the size, increase the capacity, and improve the performance of multilayer ceramic capacitors for chip parts. As an effective means, it is known that the internal electrode layer and the dielectric layer are made thin and multi-layered.

In general, a multilayer ceramic capacitor is manufactured as follows.
First, in order to form a dielectric layer, a dielectric green comprising a perovskite-type dielectric ceramic powder such as barium titanate (BaTiO ₃ ) as a green sheet ceramic powder and an organic binder such as polyvinyl butyral as a binder resin for a green sheet. On the surface of the sheet, a conductive paste containing conductive metal powder as a main component and dispersed in a vehicle containing a resin binder and a solvent is printed in a predetermined pattern and dried to remove the solvent, and a dry film that becomes an internal electrode Form.

  Next, the dielectric green sheets on which the dry film is formed are integrated by thermocompression bonding in a stacked state, then cut into the shape of a chip-type multilayer ceramic capacitor, and an oxidizing atmosphere of 800 ° C. or lower or a non-oxidizing atmosphere. The binder removal process is performed in an active atmosphere. Thereafter, heating and baking are performed while maintaining the maximum baking temperature at about 1250 ° C. in a reducing atmosphere so that the internal electrodes are not oxidized, and cooling to room temperature is performed to obtain a baking chip. External electrodes to be mounted as electronic parts on both ends of the obtained fired chip are formed by applying, drying and firing a conductive paste for external electrodes, and the surface of the external electrodes is completed by nickel plating or the like. Is.

  However, in the firing step, the temperature at which the dielectric ceramic powder starts to sinter is about 1200 ° C., whereas the temperature at which the sintering with the conductive metal powder such as nickel starts is lower. Due to this, a mismatch of sintering between the dielectric green sheet and the internal electrode occurred, and structural defects such as delamination (delamination) and cracks were likely to occur. In particular, as the number of stacked layers increases or the thickness of the ceramic dielectric layer decreases as the size and capacity increase, structural defects become more prominent.

  For example, if the constituent elements of the main component of the dielectric layer and the constituent elements of the dielectric powder contained in the electrode paste are greatly different, the electrical characteristics such as increased dielectric loss will be affected. In order to control the sintering / shrinkage of the internal electrode nickel paste to at least near the temperature at which sintering / shrinkage of the dielectric layer starts, it is usually a barium titanate or zirconate similar to the composition of the dielectric layer. A ceramic powder mainly composed of a perovskite oxide such as strontium is added. As a result, the sintering behavior of the nickel powder is controlled, and the mismatch of the sintering shrinkage behavior of the internal electrode layer and the dielectric layer can be controlled.

  In recent years, monolithic ceramic capacitors have been required to further reduce the thickness of internal electrode layers using nickel powder or the like in accordance with the demand for further miniaturization and large capacity. Therefore, in order to form a high-density internal electrode with a small amount of metal coating and achieve a thin layer and target capacity at the same time, the particle size of conductive metal powder such as nickel and ceramic powder used for conductive paste It is required to make it finer.

  Furthermore, if this ceramic powder cannot prevent the sintering and shrinkage of the conductive metal powder in the conductive paste, the effect of bringing the conductive paste sintering start temperature closer to the ceramic layer sintering start temperature will be weakened. As a result, problems such as delamination and cracks occur, resulting in a decrease in production yield and electrical reliability of the multilayer ceramic capacitor. Therefore, when the particle size of the conductive metal powder is made fine, it has a particle size smaller than the particle size of the conductive metal powder in order to intervene between the contacts of the conductive metal powder and delay the sintering start temperature. It is necessary to select a ceramic powder.

  Moreover, in order to make it possible to obtain a large capacitance, it is desired to suppress the ceramic powder to an amount as small as possible. The reason is that, firstly, the sintering diffusion of the ceramic particles for the green sheet in the dielectric layer and the ceramic particles in the internal electrode is minimized, and the electrical characteristics such as dielectric loss and dielectric breakdown voltage are not deteriorated. Does not deteriorate the capacity-temperature characteristics. Second, by increasing the conductive metal content per electrode unit area, the effective area of the internal electrode is increased without deteriorating the continuity of the internal electrode film.

  In such a technical background, in Patent Document 1, ceramic powder having an average particle size smaller than the average particle size of the conductive metal powder is used as a conductive paste capable of forming a dense film-shaped conductor on a ceramic substrate. The conductive paste used is shown.

  Patent Document 2 discloses a technique for suppressing the sintering of conductive metal particles using a conductive paste containing two types of ceramic powders. Patent Document 3 discloses a technique of conductive paste relating to high-speed firing.

JP 2002-245874 A Japanese Patent Laid-Open No. 2005-135821 JP 2009-081033 A

  However, if a ceramic powder having a particle size smaller than that of the conductive metal powder as disclosed in Patent Document 1 is selected, a sufficient effect as a sintering inhibitor cannot be obtained. If the effect cannot be obtained, a difference in shrinkage occurs between the ceramic layer and the conductive layer, and there remains a problem that defects such as cracks and delamination are likely to occur.

Patent Document 2 effectively suppresses the sintering of conductive metal powder and approximates the sintering shrinkage behavior of the dielectric layer as much as possible to prevent structural defects and electrode discontinuities. The technology of the conductive paste capable of forming an extremely thin internal electrode, which has been difficult in the past, has been disclosed, but the relationship between the firing conditions of the green sheet laminate and the composition of the conductive paste is considered. It has not been.
Further, Patent Document 3 discloses a technique of conductive paste relating to high-speed firing (higher temperature rise rate), but there are cases where ceramic powder is excessively added to the internal electrode, and the obtained multilayer ceramic electronic component There is a possibility of deteriorating the electrical characteristics of the.

  Therefore, in order to solve such problems, the present invention uses a conductive paste capable of ensuring continuity of internal electrodes, suppressing variation in capacitance, and reducing dielectric loss, and this conductive paste. The object is to provide a multilayer ceramic capacitor.

In view of such a situation, the first invention of the present invention is a method for producing a conductive paste for multilayer ceramic electronic parts comprising ceramic powder, conductive metal powder and binder resin, and has an average particle size of 0.1 μm to A green sheet laminate formed by laminating a green sheet containing a green sheet ceramic powder and a green sheet binder resin having a conductive metal powder of 0.4 μm and printed on the surface thereof with the conductive paste for multilayer ceramic electronic components. When the body is fired, the firing conditions in the firing are a temperature rise gradient and a temperature rise time from the highest temperature in the debinder firing process to the highest firing temperature after the debinder firing process, and 100 parts by weight of the nickel powder. The relationship of the addition amount of the ceramic powder has any one of the following relationships (c) to (e): A method for producing a layer ceramic electronic component electrically conductive paste.

( C). When the temperature rising gradient exceeds 600 ° C./hour and is 2400 ° C./hour or less and the temperature rising time (minutes) is “62.5− (37.5 / 1800) × temperature rising gradient” , the ceramic powder The addition amount is 10 parts by weight or more and 15 parts by weight or less.
(D). When the temperature rising gradient exceeds 2400 ° C./hour and is 5000 ° C./hour or less and the temperature rising time (minute) is “18.5-0.0025 × temperature rising gradient” , the amount of ceramic powder added is 7 .5 parts by weight or more and 10 parts by weight or less.
(E). When the temperature rising gradient exceeds 5000 ° C./hour and is 10000 ° C./hour or less and the temperature rising time (minute) is “9-0.0006 × temperature rising gradient” , the amount of ceramic powder added is 5 parts by weight. Above, 7.5 parts by weight or less.

According to a second aspect of the present invention, there is provided a method for producing a conductive paste for multilayer ceramic electronic parts, wherein the ceramic powder according to the first aspect has an average particle size of 0.01 to 0.1 μm.

According to a third aspect of the present invention, there is provided a method for producing a conductive paste for multilayer ceramic electronic parts, wherein the conductive metal powder in the first and second aspects is nickel powder or nickel alloy powder.

  According to a fourth aspect of the present invention, a conductive paste for a multilayer ceramic electronic component is printed on the surface of a green sheet containing a ceramic powder for a green sheet and a binder resin for a green sheet. A method for manufacturing a multilayer ceramic electronic component produced by firing a green sheet laminate formed by laminating printed green sheets, wherein the conductive paste for the multilayer ceramic electronic component is the first to third inventions. A method for producing a multilayer ceramic electronic component, comprising the conductive paste for a multilayer ceramic electronic component according to any one of the above.

  According to a fifth aspect of the present invention, there is provided a multilayer ceramic capacitor produced by using the perovskite type dielectric ceramic powder as a ceramic powder for a green sheet and produced by the method for producing a multilayer ceramic electronic component according to the fourth aspect. It is a manufacturing method.

The conductive paste according to the present invention is suitable for use in a small and thin multilayer ceramic electronic component, particularly a multilayer ceramic capacitor, and ensures the continuity of the internal electrode and its capacitance and dielectric breakdown voltage. This has the effect of reducing the dielectric loss by suppressing the variation of the.
In addition, by appropriately selecting the firing conditions, an electronic component such as a multilayer ceramic capacitor with few ceramic particles contained in the internal electrode and excellent electrical characteristics can be obtained.
Furthermore, the multilayer ceramic capacitor according to the present invention has small variations in capacitance and dielectric breakdown voltage, and can be easily reduced in size and thickness.

It is a calcination temperature profile in a calcination process.

The conductive paste of the present invention is obtained by dispersing conductive metal powder and ceramic powder in a vehicle in which a resin binder is dissolved in an organic solvent.
The details of the configuration will be described below using an example in which a nickel paste using nickel powder as a conductive metal powder and a multilayer ceramic electronic component are used as a multilayer ceramic capacitor.

[Conductive metal powder]
As the conductive metal powder used in the present invention, conventionally used metal powders such as nickel, copper, cobalt, silver, palladium, gold, platinum, alloy powders and composite powders mainly composed of these metals, etc. One or more commonly used conductive metal powders are used.
In the multilayer ceramic capacitor, a conductive metal powder mainly composed of palladium or nickel is desirable from firing with a dielectric green sheet. In particular, conductive metal powder containing nickel as a main component, for example, nickel powder, alloy powder or composite powder containing nickel as a main component, and mixed powder are more preferably used.

  Next, the average particle diameter of the nickel powder is set to 0.1 μm to 0.4 μm. First, the nickel powder may generate coarse particles due to aggregation, and the average particle diameter exceeds 0.4 μm. Coarse particles having a particle size exceeding 1 μm may be contained. Such coarse particles inhibit the smoothness of the dried film obtained from the conductive paste and the metal film after firing. This is unsuitable for the internal electrode of a multilayer ceramic capacitor.

  In the present invention, the particle diameter of the nickel powder is represented by the particle diameter calculated based on the BET method unless otherwise specified, and the calculation formula is shown in the following formula (1).

  The coarse particles of the nickel powder can be confirmed with an electron microscope such as SEM, but can also be confirmed with a known particle size distribution measuring apparatus.

The nickel powder can be produced by a liquid phase reduction method or a gas phase method.
The liquid phase reduction method is a method in which an aqueous nickel salt solution is reduced with a reducing agent to deposit nickel powder.
The gas phase reduction method is roughly classified into a PVD method (Physical Vapor Deposition) and a CVD method (Chemical Vapor Deposition).

In this PVD method, a sample made of nickel and the target metal or alloy is prepared, and the sample is evaporated by heat of direct current or alternating current arc discharge, high frequency induction plasma, microwave plasma, high frequency induction heating, laser, etc., and rapidly cooled. This is a method for obtaining a powder.
On the other hand, the CVD method is a method for producing nickel powder by reacting raw materials of nickel compounds such as chlorides or carbonate compounds. For example, a microreactor is used for the production of metal powder by the CVD method.

[Ceramic powder]
The ceramic powder added to the conductive paste of the present invention can be selected from BaTiO ₃ which is usually a perovskite type oxide, and those obtained by adding various additives thereto, and the dielectric powder of the multilayer ceramic capacitor. The same composition as the ceramic powder used as the main component of the green sheet forming the layer or a similar composition is also preferred. Hereinafter, an example in which BaTiO ₃ is used for the ceramic powder will be described.

  There are various methods for producing a ceramic powder, such as a solid phase method, a hydrothermal synthesis method, an alkoxide method, a sol-gel method, and the hydrothermal synthesis method is used in the present invention because a fine and sharp particle size distribution can be obtained. The ceramic powder is preferable.

The average particle size of the ceramic powder in the present invention is preferably in the range of 0.01 μm to 0.1 μm.
When the average particle diameter exceeds 0.1 μm, the gap between the contact points of the substantially spherical nickel powder particles is filled in the dry film because the ceramic powder is filled in the gap formed by stacking the substantially spherical nickel powder particles. It becomes difficult to enter.
Therefore, first, a desired dry film density cannot be obtained, that is, the dry film density is lowered. Second, the effect of delaying the sintering start temperature of the conductive paste to the sintering start temperature of the ceramic layer is weakened.

On the other hand, when the particle size of the ceramic powder is less than 0.01 μm, the maximum protrusion height of the protrusion caused by the decrease in the dry film density or the aggregated powder of the ceramic powder becomes 1.5 μm or more, and the dielectric layer is thinned. This also makes it difficult to produce reliability problems such as a decrease in insulation resistance and an increase in the short-circuit rate in the multilayer ceramic capacitor.
In the present invention, the particle size of the ceramic powder is represented by the particle size obtained by calculating the specific surface area based on the BET method unless otherwise specified. The following formula (2) shows a calculation formula when barium titanate powder is used as the ceramic powder.

  The content of the ceramic powder is 5 to 25 parts by weight with respect to 100 parts by weight of the conductive metal powder. a) to (e).

Here, the content of the ceramic powder is limited because, if the content of the ceramic powder is less than 5 parts by weight, for example, the sintering of the nickel powder cannot be controlled, and the internal electrode layer and the dielectric layer are sintered. The mismatch of the shrinkage behavior becomes remarkable, and further, the sintering of the internal electrode starts from a low temperature, and the difference in sintering temperature between the internal electrode layer and the dielectric layer becomes large, so that firing cracks are generated.
On the other hand, if the content of the ceramic powder exceeds 25 parts by weight, for example, the thickness of the dielectric layer expands due to sintering with the ceramic particles in the dielectric layer from the internal electrode layer, resulting in a composition shift. It adversely affects electrical characteristics such as a decrease in rate.

[Organic solvent]
The organic solvent used in the conductive paste of the present invention is a component that dissolves the resin component and has a function of stably dispersing inorganic components such as conductive metal powder in the paste. When applied (printed) onto a circuit board or the like, these powders are spread evenly and have a function of dissipating into the atmosphere by firing.

  Such organic solvents include terpineol (α, β, γ and mixtures thereof), dihydroterpineol, octanol, decanol, tridecanol, dibutyl phthalate, butyl acetate, butyl carbitol, butyl carbitol acetate, dipropylene glycol monomethyl Ether or the like can be used.

[binder]
As the binder resin for the conductive paste, one or more organic resins such as methylcellulose, ethylcellulose, nitrocellulose, acrylic and polyvinyl butyral are selected and used.
The amount of resin in the paste is desirably 1.0 to 5.0 wt%, and more preferably 2.0 to 4.0 wt%. If it is less than 1.0 wt%, it is difficult to obtain a viscosity suitable for screen printing, and if it exceeds 5.0 wt%, the amount of residual carbon increases at the time of binder removal, which causes delamination of the laminated chip, which is not preferable.

  In order to further adjust the viscosity, aromatic hydrocarbons and aliphatic hydrocarbons are used as diluents. For example, an aliphatic hydrocarbon such as decane, nonane, heptane, etc., a melting point of 190 to 350 ° C., preferably an aliphatic higher alcohol having 8 to 20 carbon atoms, such as decanol, octanol, etc., or an aromatic hydrocarbon such as benzene Toluene or the like can be used alone or in combination, and functions to adjust the drying speed after printing the conductive paste or to impart appropriate viscosity characteristics to the conductive paste.

  Moreover, you may add a well-known additive with conductive paste, such as an antifoamer, a dispersing agent, a plasticizer, surfactant, a thickener, to an electrically conductive paste as needed.

  For producing the conductive paste, a known method such as a three-roll mill or a ball mill can be used, and the conductive paste is printed (applied) by a known screen printing.

[Dry film]
Usually, a conductive paste is applied to the surface of a green sheet or the like by screen printing and dried by heating to remove the organic solvent to form a dry film for internal electrodes having a predetermined pattern. This dry film thickness is achieved by controlling the thickness of the screen pattern.

[Green sheet laminate and firing]
The dielectric green sheet has a thickness of 0.5 μm to 3 μm, and has a perovskite oxide BaTiO ₃ as a main component and a known inorganic additive for dielectric properties and sinterability is added to the binder resin. As a sheet, a polyvinyl butyral resin and a known plasticizer for maintaining flexibility are mixed to form a sheet.

  The conductive paste printed on the surface of the dielectric green sheet is dried by heating to remove the organic solvent contained therein to form a dry film. After forming the laminated body which laminated | stacked the dielectric green sheet in which this dry film was formed in the multilayered state by thermocompression bonding, it cut | judged in the shape of a laminated ceramic capacitor, and becomes a green sheet laminated body.

Next, the green sheet laminate is fired.
The firing process includes a binder removal process for removing the binder contained in the green sheet and the conductive paste, and a sintering process for sintering the dielectric ceramic powder and the conductive metal powder.

  In the debinding process, the maximum temperature of the debinding process is 300 ° C., and at most 800 ° C. or less, in consideration of both sides such as the prevention of oxidation of the internal electrode and the reduction of the amount of residual carbon. Etc. are appropriately selected and implemented.

  After the debinding process, the temperature is raised to a firing maximum temperature of 1150 ° C. to 1300 ° C. in an inert atmosphere or a reducing atmosphere, and the process proceeds to a sintering process in which the dielectric ceramic powder or conductive metal powder is sintered.

In general, the sintering / shrinking temperature of conductive metal powder such as nickel powder is lower than that of dielectric ceramic powder.
That is, when the green sheet laminate is fired, the conductive metal powder such as the nickel powder of the internal electrode starts to sinter / shrink before the dielectric ceramic powder of the green sheet in the process of increasing the temperature. . Since a considerable mismatch occurs between the internal electrode and the dielectric ceramic, structural defects such as delamination (delamination) and cracks occur.
Therefore, in addition to the conductive metal powder, ceramic powder for apparently shifting the sintering / shrinking temperature of the conductive metal powder to the high temperature side is mixed in the conductive paste forming the internal electrode.

  On the other hand, if the temperature rising conditions from the binder removal process to the sintering process can be accelerated, the sintering start temperature of the conductive metal powder and the dielectric ceramic powder approaches, and the internal electrode and the dielectric ceramic are considerably separated. Mismatches are eliminated, and structural defects such as delamination (delamination) and cracks can be made difficult to occur.

By the way, the ceramic powder contained in the dry film of the conductive paste may diffuse into the ceramic layer (dielectric layer) formed from the green sheet in the process of firing the green sheet laminate.
When the ceramic powder contained in this conductive paste is excessive with respect to the firing conditions (temperature rising conditions), the diffusion of the ceramic powder of the conductive paste into the ceramic layer (dielectric layer) formed from the green sheet is not It is remarkable. As the ceramic powder contained in the conductive paste, a ceramic powder having the same composition as that of the green sheet ceramic powder or a composition close to the electrical characteristics or a material close to the electrical characteristics is used. However, the diffused ceramic powder affects the green sheet.
As a result, when the ceramic powder contained in the conductive paste diffuses into the ceramic layer (dielectric layer) formed from the green sheet, the ceramic layer (dielectric layer) formed from the green sheet varies from the design specifications. For this reason, the electrical characteristics of the multilayer ceramic electronic component may deteriorate, which may cause fear that a predetermined capacitance cannot be realized.

Furthermore, from the viewpoint of sintering and shrinking of the conductive metal powder, the entire internal electrode obtained by firing the conductive paste tends to be a film that is continuously sintered between each particle of the conductive metal powder. Thus, excess ceramic powder is eliminated by sintering of the conductive metal particles. However, if the temperature rising condition is slow, neighboring conductive metal particles are sintered and ceramic particles can be scattered on the internal electrodes, so that an appropriate amount of ceramic particles can remain on the internal electrodes.
As described above, the ceramic particles excluded from the internal electrode diffuse into the ceramic layer (dielectric layer) formed from the green sheet.

Therefore, if the average particle size of the conductive metal powder is 0.1 μm to 0.4 μm, the firing condition when firing the green sheet laminate is the temperature rise to the maximum firing temperature in the firing process after the debinder firing process. The gradient and the ratio of the ceramic powder contained, that is, the addition amount of the ceramic powder with respect to 100 parts by weight of the conductive metal powder are blended in the relationship shown in Table 1 above.
In the temperature gradient where the temperature gradient after the binder removal process exceeds 600 ° C./hour, the inclusion of the ceramic powder containing the conductive paste from the continuity of the internal electrode film obtained by sintering the conductive metal powder. It is necessary to review the amount.

  So far, the present invention has been described by taking a multilayer ceramic capacitor as an example. However, it goes without saying that the present invention can also be applied to multilayer ceramic electronic components such as chip inductors.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
Using nickel powder obtained by the vapor phase reduction method having an average particle size of 0.2 μm as the conductive metal powder, with respect to 100 parts by weight of this nickel powder, the amount of addition shown in Table 2 is used for BaTiO having an average particle size of 0.06 μm. ₃ powders were weighed, and then a vehicle in which ethylcellulose was 3 parts by weight, 0.5 parts by weight of an acid organic dispersant, and 40 parts by weight of a viscosity modifier (made by Idemitsu Kosan Co., Ltd., A Solvent) were weighed. These were stirred and mixed, and kneaded with a three-roll mill to obtain a conductive paste.

  The obtained conductive paste was filtered with a filter with 99% cut filtration accuracy and an opening of 3 μm or less, printed on a green sheet so as to have a dry film thickness of 1.5 μm, and evaluated by laminating. .

The green sheet used has a thickness of 2 μm, contains BaTiO ₃ which is a perovskite oxide as a main component, and contains polyvinyl butyral resin as a binder resin.

100 layers of green sheets on which conductive paste was printed were laminated, and the fired multilayer ceramic capacitor was cut so as to have a length of 1 mm and a width of 0.5 mm (1005 size), followed by debinding and firing.
The debinding was performed in a primary debinding step of holding at 280 ° C. for 6 hours under an air atmosphere and a secondary debinding step of holding at 700 ° C. for 2 hours under a nitrogen atmosphere after the completion of the primary debinding step.

After the secondary debinding step was completed, firing was performed at a firing maximum temperature of 1200 ° C. and the firing atmosphere was maintained for 1 hour under a mixed atmosphere of nitrogen and hydrogen. FIG. 1 shows a profile of the firing temperature at the time of firing.
The “temperature increase gradient (described in Table 3)” in the examples is the temperature increase rate when the temperature gradient during temperature increase from 700 ° C. to 1200 ° C. is changed as shown in FIG.

  After firing according to the firing profile of FIG. 1, external electrodes that are terminals of the multilayer ceramic capacitor were formed, and the connection between the internal electrodes and the external electrodes was evaluated by measuring electrical characteristics and observing a cross section.

The capacitance C (unit: μF) was measured at 25 ° C. with a digital LCR meter (4278A manufactured by YHP) under the conditions of applying a frequency of 1 kHz and a measurement voltage of 1 Vrms.
The capacitance shortage was evaluated by comparing the capacitance expected from the area of the internal electrode of the multilayer ceramic capacitor and the dielectric constant of the dielectric layer with the measured capacitance.
The breakdown voltage of the multilayer ceramic capacitor was evaluated by applying 100 V to both ends of the external electrode. The case where it did not break even when 100 V was applied was judged as OK.
The evaluation results are shown in Table 3.

  As is clear from Table 3, when the relationship between the temperature rising gradient in the firing process and the content of the ceramic powder is within the scope of the present invention, both capacitance, breakdown voltage, and connectivity with external electrodes are Although good results have been obtained, it is shown that one of the characteristics is degraded when the relationship is out of the range.

Claims (5)

A method for producing a conductive paste for multilayer ceramic electronic parts comprising ceramic powder, conductive metal powder and binder resin,
Having conductive metal powder with an average particle size of 0.1 μm to 0.4 μm,
When firing a green sheet laminate formed by laminating a green sheet containing a green sheet ceramic powder and a green sheet binder resin printed with the conductive paste for multilayer ceramic electronic components on the surface, firing conditions in the firing However, the relationship between the temperature rise from the maximum temperature in the debinder firing process to the maximum firing temperature after the debinder firing process and the temperature rise time and the amount of the ceramic powder added to 100 parts by weight of the conductive metal powder, The manufacturing method of the electrically conductive paste for multilayer ceramic electronic components characterized by having the relationship in any one of following (c)-(e).
(C). When the temperature rising gradient exceeds 600 ° C./hour and is 2400 ° C./hour or less and the temperature rising time (minutes) is “62.5− (37.5 / 1800) × temperature rising gradient” , the ceramic powder The addition amount is 10 parts by weight or more and 15 parts by weight or less.
(D). When the temperature rising gradient exceeds 2400 ° C./hour and is 5000 ° C./hour or less and the temperature rising time (minute) is “18.5-0.0025 × temperature rising gradient” , the amount of ceramic powder added is 7 .5 parts by weight or more and 10 parts by weight or less.
(E). When the temperature rising gradient exceeds 5000 ° C./hour and is 10000 ° C./hour or less and the temperature rising time (minute) is “9-0.0006 × temperature rising gradient” , the amount of ceramic powder added is 5 parts by weight. Above, 7.5 parts by weight or less. 2. The method for producing a conductive paste for multilayer ceramic electronic component according to claim 1, wherein the ceramic powder has an average particle size of 0.01 to 0.1 μm. The method for producing a conductive paste for a multilayer ceramic electronic component according to claim 1, wherein the conductive metal powder is nickel powder or nickel alloy powder. A conductive paste for multilayer ceramic electronic parts is printed on the surface of the green sheet containing the ceramic powder for green sheets and the binder resin for green sheets, and the green sheet on which the conductive paste for multilayer ceramic electronic parts is printed is laminated. A method for producing a multilayer ceramic electronic component for firing a formed green sheet laminate,
The method for manufacturing a multilayer ceramic electronic component, wherein the conductive paste for a multilayer ceramic electronic component is the conductive paste for a multilayer ceramic electronic component according to any one of claims 1 to 3.   A method for producing a multilayer ceramic capacitor, wherein a perovskite-type dielectric ceramic powder is used for the ceramic powder for a green sheet and is produced by the method for producing a multilayer ceramic electronic component according to claim 4.