JP2018037630A - Paste for internal electrodes, method for manufacturing the same, and multilayer ceramic capacitor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a paste for an internal electrode having higher adhesion by preventing peeling and positional deviation between internal electrode layers during manufacturing of a multilayer ceramic capacitor. SOLUTION: The paste for an internal electrode is a paste for an internal electrode containing a conductive powder, a ceramic powder, an ethyl cellulose resin, a polyvinyl butyral resin, an organic solvent and an anionic surfactant, and the polyvinyl butyral resin is the total amount of the paste. The anionic surfactant has at least one carboxyl group (COOH group) and is contained in an amount of 1% by mass or more and 2.5% by mass or less, and is 0 with respect to 100 parts by mass of the conductive powder. It is contained in an amount of 1 part by mass or more and 6.5 parts by mass or less, and contains glycol in a range of more than 0.5 mol times and less than 3 mol times with respect to the carboxyl group (COOH group) of the anionic surfactant. [Selection diagram] Fig. 1

Description

  The present invention relates to an internal electrode paste, a manufacturing method thereof, and a multilayer ceramic capacitor.

  A multilayer ceramic capacitor conventionally used as one of electronic components generally has a structure in which dielectric layers and internal electrode layers are alternately stacked. In recent years, with the miniaturization and high performance of electrical and electronic devices, there has been an increasing demand for miniaturization and large capacity for multilayer ceramic capacitors. As a multilayer ceramic capacitor that meets such requirements, multilayering by thinning the dielectric layer and the internal electrode layer is important.

The multilayer ceramic capacitor is produced, for example, by the following manufacturing method. First, a dielectric green sheet (hereinafter also referred to as “green sheet”) containing a dielectric powder such as barium titanate (BaTiO ₃ ) and an organic binder contains conductive metal particles and an organic binder. The internal electrode paste to be applied is applied according to the desired internal electrode pattern and dried. Next, after the dried internal electrode pattern / green sheet (hereinafter also referred to as “internal electrode layer / dielectric layer”) is laminated and pressure-bonded so that the internal electrode layers and the dielectric layers are alternated, Thermocompression bonding is performed, and the obtained thermocompression bonded body is cut into a desired size. The cut crimped body is heated at a predetermined temperature and atmosphere in order to remove the organic binder. Thereafter, firing is performed to integrally sinter the internal electrode layer and the dielectric layer to obtain a multilayer ceramic capacitor element body. The obtained multilayer ceramic capacitor body is barrel-polished on both end faces to expose the internal electrodes, and then external electrode paste is applied to the polished end faces, baked and attached to the surface of the attached external electrodes. The product is made by plating.

  By the way, the paste for internal electrodes of the conventional multilayer ceramic capacitor uses, for example, ethyl cellulose resin as the organic binder and mainly terpineol as the organic solvent. However, when a pressure-bonded body is produced by the above-described manufacturing method using such an internal electrode paste, the adhesion between the internal electrode layer and the dielectric layer is poor, and delamination may occur.

  For example, Patent Document 1 discloses an internal electrode paste containing at least conductive metal particles, a co-material, a resin, an organic solvent, and an organic additive. This internal electrode paste is a compound in which the co-material is a main constituent material of a green sheet, the resin contains at least a polyvinyl butyral resin, and the organic additive has a functional group showing an acid value and a functional group showing an amine value And / or the use of a mixture of a compound having a functional group exhibiting an acid value and a compound having a functional group exhibiting an amine value improves the pressure-bonding property between the internal electrode layer and the dielectric layer. Yes.

JP 2004-200450 A

  However, according to the inventor's study, in an internal electrode paste containing polyvinyl butyral resin, when an anionic surfactant having a carboxyl group (COOH group) is used as an organic additive, the internal electrode layer and the dielectric layer It became clear that the adhesiveness of the resin sometimes deteriorated. Although this reason is not limited, it is thought that it is because the hydrogen bond of an internal electrode layer and the polyvinyl butyral resin in a dielectric material layer is inhibited by the COOH group of anionic surfactant.

  In view of such circumstances, an object of the present invention is to provide an internal electrode paste with higher adhesion by preventing peeling and misalignment between internal electrode layers during the production of a multilayer ceramic capacitor.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the mol of COOH groups contained in the anionic surfactant in the internal electrode paste is improved in order to improve the adhesion between the internal electrode layer and the dielectric layer. The inventors have found that the above problem can be solved by adding a specific amount of glycol with respect to the amount, and have completed the present invention.

  In the first aspect of the present invention, an internal electrode paste containing conductive powder, ceramic powder, ethyl cellulose resin, polyvinyl butyral resin, an organic solvent and an anionic surfactant, the polyvinyl butyral resin is added to the total amount of the paste. On the other hand, it is contained in an amount of 1% by mass to 2.5% by mass, and the anionic surfactant has at least one or more carboxyl groups (COOH groups), and is contained in an amount of 0.1% to 100 parts by mass of the conductive powder. An internal electrode paste that is contained in an amount of 1 to 6.5 parts by mass and contains glycol in a range of more than 0.5 mol and less than 3 mol with respect to the carboxyl group (COOH group) of the anionic surfactant. Is provided.

  Moreover, it is preferable that the boiling point of glycol is 300 degrees C or less. The glycol is preferably at least one selected from ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. The conductive powder preferably has an average particle size of 0.05 μm or more and 0.5 μm or less. The anionic surfactant preferably has 16 to 22 carbon atoms. Moreover, it is preferable that an organic solvent contains the 1st organic solvent and the 2nd organic solvent which has a boiling point lower than a 1st organic solvent. In addition, the first organic solvent preferably has a boiling point of 150 ° C. or higher and 300 ° C. or lower, and the second organic solvent preferably has a boiling point of 120 ° C. or higher and 250 ° C. or lower. Moreover, it is preferable to contain the said glycol in the range of 0.5 mass% or more with respect to 100 mass% of total amounts of electroconductive powder, ceramic powder, an organic binder, and an organic solvent.

  In the second aspect of the present invention, an organic vehicle is prepared by mixing an organic binder and an organic solvent, and conductive powder, ceramic powder, an anionic surfactant, and glycol are added to the organic vehicle. The anionic surfactant has at least one carboxyl group (COOH group), and is 0.1 part by mass or more and 6.5 parts by mass with respect to 100 parts by mass of the conductive powder. Production of paste for internal electrodes, added in a range of less than or equal to part by mass, and glycol added in a range of more than 0.5 mol and less than 3 mol with respect to the carboxyl group (COOH group) of the anionic surfactant A method is provided.

  According to a third aspect of the present invention, there is provided a multilayer ceramic capacitor comprising a laminate in which dielectric layers and internal electrode layers are alternately laminated, wherein the internal electrode is formed using the internal electrode paste. A multilayer ceramic capacitor is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the paste for internal electrodes which is excellent in the dispersibility of electroconductive powder, and is excellent in adhesiveness with a dielectric material layer, and its manufacturing method can be provided.

It is a figure which shows an example of the manufacturing method of the paste for internal electrodes which concerns on embodiment. It is a figure which shows an example of the preparation method of an organic vehicle. It is a figure which shows an example of the multilayer ceramic capacitor which concerns on embodiment.

  Hereinafter, a configuration example of the multilayer ceramic capacitor internal electrode paste of the present embodiment will be described. The present invention is not limited to the following embodiments. Various modifications and substitutions can be made to the following embodiments without departing from the scope of the present invention.

[Internal electrode paste]
The multilayer ceramic capacitor internal electrode paste (hereinafter also simply referred to as “internal electrode paste”) contains at least a conductive powder, a ceramic powder, a polyvinyl butyral resin, an ethyl cellulose resin, an organic solvent, and a glycol. To do. Hereinafter, each component will be described.

(Conductive powder)
The internal electrode paste of the present embodiment includes a conductive powder. By adding conductive powder, conductivity can be imparted to the internal electrode formed using the internal electrode paste. The conductive powder is not particularly limited, and for example, one or more powders selected from Ni, Cu, Pd, Ag, and alloys thereof can be used. For example, when a powder containing Ni as a main component (hereinafter also simply referred to as “nickel powder”) is used, the conductivity, corrosion resistance, and cost are excellent. Nickel powder includes Ni powder and Ni-based alloy powder. As the Ni alloy powder, for example, an alloy powder of nickel and at least one element selected from the group consisting of manganese, chromium, cobalt, aluminum, iron, copper, zinc, silver, gold, platinum and palladium is used. it can. The content of Ni in the alloy powder containing Ni as a main component is, for example, 50% by mass or more, and preferably 80% by mass or more. In addition, for example, nickel powder containing about several hundred ppm of S (sulfur) may be used in order to suppress rapid gas generation due to partial thermal decomposition of the organic binder during the binder removal treatment. .

  The particle size of the conductive powder is not particularly limited. Dispersibility in the paste for internal electrodes, operability when applied to a green sheet, etc., conductivity when fired to form internal electrodes, etc. Can be arbitrarily selected. When used in a multilayer ceramic capacitor having a high lamination and a high capacity, for example, the average particle size of the conductive powder is preferably 0.05 μm or more and 0.5 μm or less. In addition, the average particle diameter of this electroconductive powder is a value calculated | required from a scanning electron microscope (SEM) photograph, and means the particle diameter in the integrated value 50% in a particle size distribution. In the present specification, the average particle size of the conductive powder has the same meaning in other portions.

  When the average particle size of the conductive powder is 0.5 μm or less, the multilayer ceramic capacitor can be particularly thinned. Moreover, the internal electrode paste of the present embodiment is excellent in dispersibility and adhesion even when, for example, the average particle size of the conductive powder is 0.4 μm or less or 0.3 μm or less. On the other hand, when the average particle diameter of the conductive powder is 0.05 μm or more, it is possible to suppress the surface activity of the conductive powder from becoming higher than necessary, and to prevent the viscosity of the internal electrode paste from increasing. In this case, deterioration or the like can be suppressed when stored for a long period of time as an internal electrode paste.

  The content of the conductive powder in the internal electrode paste is not particularly limited, and is arbitrarily selected according to the viscosity required for the internal electrode paste, the electrical conductivity required for the internal electrode, and the like. can do. For example, the internal electrode paste preferably contains 30% by mass to 70% by mass, and more preferably 40% by mass to 60% by mass of the conductive powder with respect to the total amount of the internal electrode paste.

  When the content of the conductive powder in the internal electrode paste is 30% by mass or more, it is possible to sufficiently ensure the electrode film forming ability when firing the internal electrode paste, and to obtain a desired capacitor capacity more reliably. be able to. On the other hand, when the content of the conductive powder in the internal electrode paste is 70% by mass or less, the electrode film of the internal electrode can be easily thinned.

(Organic binder)
The internal electrode paste contains ethyl cellulose resin and polyvinyl butyral resin as organic binders. An organic binder can be made into the mixed system which consists of ethylcellulose resin and polyvinyl butyral resin, for example. The ethyl cellulose resin has good solubility in a solvent, printability, combustion decomposability, and the like, and can be suitably used as a binder for an internal electrode paste. Polyvinyl butyral resin is a resin generally used for green sheets. The organic binder may contain a small amount of other resins as long as the effects of the present invention are not impaired.

  For example, the polyvinyl butyral resin can be contained in an amount of 1% by mass to 2.5% by mass with respect to the total amount of the internal electrode paste. When the content of the polyvinyl butyral resin is in the above range, the adhesion strength between the green sheet and the dry film of the internal electrode paste can be increased. The reason why the adhesion strength increases is not particularly limited, but when the internal electrode layer and the dielectric layer are subjected to thermocompression bonding in the production process of the multilayer ceramic capacitor, the hydroxyl group of the polyvinyl butyral resin contained in the internal electrode layer ( It is considered that the hydrogen bond due to (OH group) is imparted to the adhesion to the dielectric layer.

  The content of the organic binder in the internal electrode paste is not particularly limited and can be arbitrarily selected. The total content of the organic binder is, for example, that the content of the conductive powder is 100 parts by mass, and the content of the organic binder is preferably 1 part by mass or more and 7 parts by mass or less, and 1.5 parts by mass or more More preferably, it is 6 parts by mass or less. When content of the said organic binder is 1 mass part or more, it can suppress that the organic solvent in the paste for internal electrodes osmose | permeates the green sheet side, and can suppress sheet | seat attack more reliably. When the content of the organic binder is 7 parts by mass or less, the debinding property of the internal electrode paste can be particularly improved. In addition, when an organic binder consists of polyvinyl butyral resin and ethyl cellulose resin, content of the whole organic binder becomes a sum total of content of these both resin.

  The content of the ethyl cellulose resin and the polyvinyl butyral resin in the organic binder is not particularly limited and can be set to any ratio. For example, a mass ratio of (content of polyvinyl butyral resin) / (content of ethyl cellulose resin) is preferably 0.2 or more, and more preferably 0.6 or more. When the mass ratio is in the above range, the adhesion between the green sheet and the dry film of the internal electrode paste is particularly excellent. On the other hand, the mass ratio of (content of polyvinyl butyral resin) / (content of ethyl cellulose resin) is, for example, preferably 5 or less, and more preferably 4 or less. When this mass ratio is in the above range, it is excellent in solubility in a solvent, printability, and combustion decomposability.

(Organic solvent)
The internal electrode paste contains an organic solvent. For example, the organic solvent dissolves the organic binder or adjusts the paste viscosity. The organic solvent is not particularly limited, and a conventionally known solvent can be appropriately selected and used. Moreover, the organic solvent may use 1 type and may use 2 or more types. In addition, it is preferable that the boiling point of an organic solvent exceeds 100 degreeC, for example. If the boiling point of the solvent is 100 ° C. or lower, there is a risk of evaporation during paste production.

  Examples of the organic solvent include terpene solvents such as terpineol and dihydroterpineol, dihydroterpinel acetate, isobornyl acetate, isobornyl propionate, isobornyl butyrate, isobornyl isobutyrate and the like. .

  Moreover, when the organic solvent mentioned above is used as the first organic solvent, the organic solvent is preferably used in combination of two or more kinds of organic solvents such as a second organic solvent having a boiling point lower than that of the first organic solvent. . In the production process of the multilayer ceramic capacitor, the internal electrode paste is continuously printed as an internal electrode pattern on a plurality of green sheets using a printing apparatus. At this time, if the drying speed of the internal electrode paste is fast, the organic solvent in the internal electrode paste is lost while the internal electrode pattern is printed, and the viscosity of the internal electrode paste increases, and the internal electrode pattern Printing may be difficult. By combining two or more organic solvents having different boiling points, the drying speed can be easily adjusted to a suitable range, and the increase in the viscosity of the internal electrode paste during printing as described above can be suppressed. . The second organic solvent preferably has a lower viscosity than the first organic solvent.

The boiling point of the first organic solvent is preferably 150 ° C. or higher and 300 ° C. or lower, and more preferably 180 ° C. or higher and 250 ° C. or lower. When the boiling point is lower than 150 ° C., the drying property is high, the drying proceeds in the printing process, and the viscosity tends to increase. On the other hand, when the boiling point is 300 ° C. or higher, the drying property is poor and the solvent tends to remain in the drying process. When the organic solvent contains the first organic solvent, the drying rate is moderately slowed, and the printability of the internal electrode paste is further improved.
Examples of the first organic solvent include terpene solvents such as terpineol and dihydroterpineol, and isobornyl acetate.

  For example, the boiling point of the second organic solvent is desirably 120 ° C. or higher and 250 ° C. or lower, and more preferably 150 ° C. or higher and 220 ° C. or lower. When the boiling point is lower than 120 ° C., the drying property is high, so that drying proceeds in the printing process and the viscosity tends to increase. On the other hand, when the boiling point is 250 ° C. or higher, since the drying property is poor, the solvent tends to remain in the drying process. When the organic solvent contains the second organic solvent, the paste viscosity can be easily adjusted. When one kind of terpene solvents such as terpineol and dihydroterpineol and isobornyl acetate is selected as the first organic solvent, the second organic solvent may be, for example, an organic compound having a boiling point lower than that of the first organic solvent. A solvent can be appropriately selected.

  Preferred examples of the second organic solvent include saturated aliphatic hydrocarbon solvents and ethylene glycol monobutyl ether acetate. As the saturated aliphatic hydrocarbon solvent, a solvent containing a saturated hydrocarbon as a main component can be preferably used, and in particular, a solvent containing tridecane, nonane, and cyclohexane can be more preferably used. In addition, a solvent containing tridecane, nonane, and cyclohexane as main components can be particularly preferably used. The main component here means that 90 vol% or more is contained by volume ratio.

  In addition, as the second organic solvent, a commercially available petroleum mixed solvent may be used, and for example, a commercially available mineral spirit or No. 0 solvent (JX Nippon Oil & Energy Corporation) may be used. Note that the second organic solvent may be one type or a mixed solvent containing two or more types as long as it has a lower boiling point than the first organic solvent.

  The content (ratio) of the first organic solvent and the second organic solvent in the organic solvent is not particularly limited and can be arbitrarily selected. The ratio of the 1st organic solvent in an organic solvent can be 20 mass% or more and less than 80 mass% with respect to the whole organic solvent, for example. The balance is the second organic solvent.

  When the ratio of the 1st organic solvent in an organic solvent is 20 mass% or more, it can suppress that the drying property of the paste for internal electrodes becomes high too much. For this reason, it is possible to prevent the viscosity of the internal electrode paste from greatly increasing during printing of the internal electrode pattern, and the internal electrode pattern can be printed stably. On the other hand, when the ratio of the first organic solvent in the organic solvent is less than 80% by mass, the internal electrode paste can be given a certain degree of drying property. For this reason, the residue of the organic solvent in the dry film | membrane of the paste for internal electrodes can be suppressed.

  The content of the organic solvent (addition amount during preparation) is not particularly limited, and can be arbitrarily selected according to the viscosity of the internal electrode paste. For example, the content of the organic solvent is preferably 60 parts by mass or more and 100 parts by mass or less, and more preferably 40 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the conductive powder.

(Ceramic powder)
The internal electrode paste of this embodiment may contain a ceramic powder. The ceramic powder is added as a sintering inhibitor, for example. The ceramic powder can be selected from, for example, BaTiO ₃ which is a perovskite oxide, and various additives added thereto. Further, as the ceramic powder, those having the same composition as or similar to the ceramic powder used as the main component of the green sheet of the multilayer ceramic capacitor are preferably used.

  The method for producing the ceramic powder is not particularly limited, and for example, ceramic powder produced by various production methods such as a solid phase method, a hydrothermal synthesis method, an alkoxide method, and a sol-gel method can be used. In particular, a ceramic powder produced by a hydrothermal synthesis method is preferably used because it has a fine and sharp particle size distribution.

The particle size of the ceramic powder is not particularly limited, but for example, the average particle size is preferably 0.01 μm or more and 0.2 μm or less. In the present specification, the average particle size of the ceramic powder is expressed by a particle size obtained by calculating the specific surface area based on the BET method unless otherwise specified. As the ceramic powder, for example, a formula for calculating the particle size [unit: m] when barium titanate powder is used is shown in the following formula (1).
Particle size = 6 / S _BT ρ _BT Formula (1)
The (wherein _{(1), S BT} represents the specific surface area of barium titanate powder ^{[m 2 / g], ρ} BT is the true density of barium titanate ^{(6.1 [g / cm 3]} ) Represents.)

  When the average particle size of the ceramic powder is 0.01 μm or more, the effect of delaying the sintering start temperature of the internal electrode paste to the sintering start temperature of the dielectric layer (sintering delay effect) can be sufficiently exerted. And the generation of structural defects such as delamination and cracks can be further suppressed. In addition, when the average particle size of the ceramic powder is in the above range, the decrease in the dry film density, which is the film density when the internal electrode paste formed into a film shape is dried, is further suppressed, and the multilayer ceramic capacitor is made thinner. As a result, the reliability of the multilayer ceramic capacitor can be improved. Further, when the average particle size of the ceramic powder is 0.2 μm or less, the ceramic powder is easily filled between the conductive powders, so that the dry film density can be sufficiently increased, and the sintering delay effect is also sufficient. Can be demonstrated.

  When the internal electrode paste contains ceramic powder, the content of the ceramic powder is not particularly limited. For example, it is 3 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the conductive powder. It is preferable to add to.

  When the content of the ceramic powder is 3 parts by mass or more, since the sintering of the conductive powder can be sufficiently controlled, the mismatch of the sintering shrinkage behavior between the internal electrode layer and the dielectric layer can be further suppressed. Further, when the content of the ceramic powder exceeds 25 parts by mass, the ceramic powder particles of the internal electrode layer are sintered with the ceramic particles in the dielectric layer, and the thickness of the dielectric layer expands to cause a compositional deviation. There is a risk of adversely affecting electrical characteristics such as a decrease in dielectric constant. For this reason, it is preferable that the content of the ceramic powder is in the above range so as not to cause adverse effects due to the electrical characteristics of the dielectric layer and the like.

(Dispersant)
The internal electrode paste contains an anionic surfactant as a dispersant. The dispersant is used for preventing aggregation of the metal powder and imparting dispersibility. An anionic surfactant has a large adsorptive power to the surface of the conductive powder, and contributes to improving the dispersibility of inorganic particles such as the conductive powder by its surface modification action. The anionic surfactant also has a function of improving the smoothness of the coating film and the density (dry film density) when the internal electrode paste film is dried. As the anionic surfactant, a carboxylic acid surfactant having a carboxyl group (COOH group) is preferable. In addition to the carboxyl group, the carboxylic acid surfactant may have a functional group such as a hydroxyl group, a carbonyl group, an acyl group, or an amino group, or a structure such as an ether bond or an amide bond. In addition, a gemini surfactant may be used as the anionic surfactant.

  Examples of the anionic surfactants include higher fatty acids such as stearic acid, oleic acid, myristic acid, palmitic acid, linoleic acid, lauric acid, and linolenic acid, and amides of higher fatty acids such as glycine and stearic acid or lauric acid. Compound etc. are mentioned. Among these, as the anionic surfactant, an anionic surfactant having 16 to 22 carbon atoms is preferable. In addition, anionic surfactant may be used by 1 type, or may use 2 or more types together.

  The content of the anionic surfactant is, for example, from 0.01 parts by weight to 8 parts by weight and preferably from 0.2 parts by weight to 7 parts by weight with respect to 100 parts by weight of the conductive powder. . When content is less than 0.2 mass part, the dispersibility of nickel powder may not be enough and a dry film density may fall. Moreover, since sufficient dispersibility can be acquired when content is 7 mass parts or less, it is not necessary to add more.

  Moreover, you may use dispersing agents other than an anionic surfactant for the paste for internal electrodes. Such a dispersant is not particularly limited, and any dispersant that can stably disperse a conductive powder or the like in a finely divided state in an organic solvent can be suitably used. An activator or the like can be used. Further, since the surface of the conductive powder containing nickel is contaminated by oxidation or the like and the chemical properties are not uniform, both an anionic surfactant and a cationic surfactant are used as the dispersant. be able to. Two or more anionic surfactants or cationic surfactants may be used in combination.

  The amount of the dispersant added is not particularly limited, and may be arbitrarily selected depending on the storage stability required for the internal electrode paste, the degree of dispersibility of the inorganic particles such as conductive powder, the type of the dispersant, and the like. You can choose. For example, when the content of inorganic particles (total of conductive powder and ceramic powder) contained in the internal electrode paste is 100 parts by mass, the additive amount of the dispersant is 0.01 parts by mass or more and 10 parts by mass or less. It is preferably 0.20 parts by mass or more and 7 parts by mass or less. An addition amount of 0.01 parts by mass or more is preferable because inorganic particles such as conductive powder and ceramic powder can be sufficiently dispersed. When the amount exceeds 10 parts by mass, the drying property of the internal electrode paste may decrease, and the density of the dry film of the internal electrode paste (dry film density) may decrease.

(Glycol)
The internal electrode paste contains a specific amount of glycol with respect to the mol amount of the carboxyl group (—COOH group) of the anionic surfactant. When the internal electrode paste contains glycol, adhesion between the internal electrode layer and the dielectric layer when a multilayer ceramic capacitor is manufactured is improved. The reason why the adhesion is improved is not limited, but the hydrogen bond between the polyvinyl butyral resin contained in the internal electrode layer and the polyvinyl butyral resin contained in the dielectric layer is caused by the carboxyl group (COOH group) of the anionic surfactant. It is assumed that inhibition is suppressed. In addition, since glycol has low volatility at room temperature, the internal electrode paste containing glycol can exhibit the above-described effects even after being stored for a long period of time. Moreover, the internal electrode paste can suppress gelation of the internal electrode paste by containing glycol.

  The boiling point of glycol is preferably 300 ° C. or lower, more preferably 250 ° C. or lower. When the boiling point of glycol exceeds 300 ° C., glycol may remain in the drying process when producing the multilayer ceramic capacitor, and the resulting dried film may have more flexibility than necessary. There is a possibility of misalignment. Further, during the debinding process, the remaining glycol may be gasified to increase the internal pressure of the laminate, which may cause cracks and the like. Although the minimum of the boiling point of glycol is not specifically limited, For example, it is 150 degreeC or more.

  Moreover, it is preferable that the boiling point of glycol is below the boiling point of an organic solvent. If the boiling point of the glycol is higher than the boiling point of the organic solvent, the glycol may remain in the drying process when producing the multilayer ceramic capacitor, and the resulting dried film may have more flexibility than necessary. There is a possibility of causing a positional deviation of the laminated body. Further, during the debinding process, the remaining glycol may be gasified to increase the internal pressure of the laminate, which may cause cracks and the like.

  As the glycol, a known dihydric alcohol can be used. For example, at least one selected from ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol can be used. Among these, for example, from the viewpoint of low boiling point, preferably at least one selected from ethylene glycol, propylene glycol, diethylene glycol and triethylene glycol can be used, and more preferably, ethylene glycol, propylene glycol and diethylene glycol. At least one selected from can be used. Further, from the viewpoint of excellent handleability, it is preferable to use at least one of ethylene glycol and propylene glycol. In addition, glycol may be used individually by 1 type and may be used in mixture of 2 or more types.

  In the internal electrode paste, glycol is contained in a range of more than 0.5 mol times and less than 3 mol times, preferably 0.8 mol times or more, relative to the mol amount of the carboxyl group (COOH group) of the anionic surfactant. It is contained in a range of 2.5 mol times or less, more preferably 1 mol times or more and 2 mol times or less. When the glycol content is in the above range, the adhesion between the internal electrode layer and the dielectric layer when producing a multilayer ceramic capacitor is further improved. On the other hand, when the content of glycol is 0.5 mol times or less, the effect of improving the adhesion between the internal electrode layer and the dielectric layer cannot be sufficiently obtained. Moreover, when the content of glycol is 3 mol times or more, the viscosity of the internal electrode paste decreases, and the density of the dry film of the internal electrode paste (dry film density) decreases.

  The internal electrode paste preferably contains glycol in a range of 0.5% by mass or more with respect to 100% by mass of the total amount of conductive powder, ceramic powder, organic binder, and organic solvent. When content of glycol is the said range, gelatinization of the paste for internal electrodes can be suppressed more. The reason why the gelation is suppressed is not limited, but, for example, a hydrogen bond is formed between the OH group present at the terminal of the ethyl cellulose resin contained in the internal electrode paste and the conductive powder (for example, nickel powder), May cause an increase in paste viscosity. It is presumed that glycol inhibits the gelation of the internal electrode paste by inhibiting the formation of this hydrogen bond. In addition, from a viewpoint of gelatinization suppression, content of glycol can be made into the range of 5 mass% or less, for example.

  Note that the addition of an organic acid can also inhibit the formation of hydrogen bonds between the ethylcellulose resin and the conductive powder, but the organic acid oxidizes the conductive powder. On the other hand, when glycol is used, oxidation of the conductive powder does not occur, the paste viscosity can be stabilized for a long period of time, and gelation can be suppressed. In addition, since glycol has low volatility at room temperature, the internal electrode paste containing glycol can exhibit the above-described effects even after being stored for a long period of time.

  The internal electrode paste contains glycol in a range of 0.5% by mass or more and 2.4% by mass or less with respect to 100% by mass of the total amount of conductive powder, ceramic powder, organic binder, and organic solvent. It is more preferable. When the content of glycol is in the above range, it is possible to achieve both high adhesion and suppression of gelation at a high level.

(Other ingredients)
The conductive paste of the present embodiment may include conventionally known additive components other than the components described above.

[Method for producing internal electrode paste]
Drawing 1 is a figure showing an example of a manufacturing method of a paste for internal electrodes concerning an embodiment. FIG. 2 is a diagram illustrating an example of a method for preparing an organic vehicle. In addition, the following description is an example of the manufacturing method of the paste for internal electrodes, Comprising: It does not limit to this method. For example, in the manufacturing method illustrated in FIG. 1, some steps may be deleted, and other steps may be added. In describing FIG. 1, FIG. 2 will be referred to as appropriate. Note that a part of the description overlapping with the matters already described in the internal electrode paste is omitted.

  The internal electrode paste manufacturing method according to the embodiment includes, for example, as shown in FIG. 1, preparing an organic vehicle by mixing an organic binder and an organic solvent (step S1), and making the organic vehicle conductive. Adding and dispersing the powder, the anionic surfactant, and the glycol (step S2).

  First, an organic vehicle is prepared by dissolving an organic binder in an organic solvent (step S1). The organic binder includes ethyl cellulose resin and polyvinyl butyral resin. As described above, the organic solvent may include a first organic solvent and a second organic solvent having different boiling points. The first organic solvent has a higher boiling point than, for example, the second organic solvent.

  The procedure for preparing the organic vehicle is not particularly limited. For example, as shown in FIG. 2A, a first organic vehicle containing a polyvinyl butyral resin and a second organic vehicle containing an ethylcellulose resin can be prepared separately. That is, the organic vehicle is prepared by mixing a polyvinyl butyral resin and an organic solvent to prepare a first organic vehicle, and mixing an ethyl cellulose resin and an organic solvent to prepare a second organic vehicle. , Can have.

  In the step of preparing the first organic vehicle, for example, polyvinyl butyral organic vehicle can be prepared by dissolving polyvinyl butyral in the first organic solvent. In the second organic vehicle preparation step, for example, the ethylcellulose organic vehicle can be prepared by dissolving ethylcellulose in the first organic solvent.

  Further, for example, as shown in FIG. 2B, a third organic vehicle containing both resins by adding polyvinyl butyral and ethyl cellulose simultaneously to the first organic solvent and / or the second organic solvent. Can be prepared.

  In addition, when an organic vehicle is prepared for each organic binder, each organic vehicle may be individually mixed with a conductive powder or the like in a dispersion step described later. Alternatively, the organic vehicles prepared in advance for each organic binder may be mixed to prepare an organic vehicle containing both resins, and then mixed with conductive powder or the like in the dispersion step.

  The organic solvent used in the organic vehicle may be, for example, a first organic solvent for one organic vehicle and a second organic solvent for the other organic vehicle. In addition, each organic vehicle is prepared using a mixed liquid of the first organic solvent and the second organic solvent, or the organic vehicle is prepared using the second organic solvent instead of the first organic solvent. The first organic solvent may be added in the dispersion step.

  Specific conditions for preparing the organic vehicle are not particularly limited. For example, the organic binder is gradually added to the organic solvent in a constant temperature bath in which the organic solvent is heated to 50 ° C. or higher and 60 ° C. or lower, and then the organic It can be prepared by heating with stirring until the binder is dissolved.

  Next, as shown in FIG. 1, conductive powder, an anionic surfactant, and glycol are added and dispersed in the organic vehicle (step S2). In the dispersion step, the organic vehicle prepared in the organic vehicle preparation step (step S1) and the conductive powder can be put into a mixer and stirred and mixed. When mixing the organic vehicle and the conductive powder, the anionic surfactant and the glycol can be mixed together.

  The order in which the conductive powder, the anionic surfactant and the glycol are added to the organic vehicle is not particularly limited, and for example, all materials can be added simultaneously. Further, after adding the conductive powder to the organic vehicle, the anionic surfactant or glycol may be added, respectively, or before adding the conductive powder to the organic vehicle, the anionic surfactant or glycol is added. It may be added. In addition, the glycol may be added to the organic vehicle after adding a conductive powder, an anionic surfactant, and optionally a ceramic powder to form a paste, and then added with stirring, for example.

  When internal electrode paste contains ceramic powder and other additive components, ceramic powder, various additives, etc. should be added when the organic vehicle and conductive powder are added to the mixer in the dispersion process. You can also. The order of mixing these components in the dispersing step is not particularly limited, and may be added simultaneously with the conductive powder, mixed and dispersed, added before or after addition of the conductive powder, mixed and dispersed. Also good.

  In addition, when an organic vehicle is prepared using only a part of the first organic solvent and the second organic solvent, which are organic solvents, the organic solvent that has not been added in the organic vehicle preparation step is also added in the dispersion step. It can be put into a mixer and stirred and mixed. For example, when an organic vehicle is prepared using only the first organic solvent, the second organic solvent can be added in the dispersion step (step S02). When the second organic solvent is added in the dispersion step, the viscosity of the internal electrode paste can be more easily adjusted.

  Moreover, it is preferable to further disperse | distribute with a three roll mill after stirring and mixing by a mixer. When a three-roll mill is used, a mixed material such as conductive powder can be dispersed and mixed more uniformly in the organic vehicle.

  The ceramic powder is preferably added in the dispersion step as described above, but may be added in steps other than the dispersion step. For example, the ceramic powder may be added with an organic solvent or an organic binder during the preparation of the organic vehicle. Further, as described above, the anionic surfactant is preferably added in the dispersion step, but may be added in a step other than the dispersion step. For example, the anionic surfactant may be added together with an organic solvent or an organic binder during the preparation of the organic vehicle.

  A multilayer ceramic capacitor described later is manufactured using the internal electrode paste of this embodiment. In the multilayer ceramic capacitor, even when the thickness of the dielectric green sheet is, for example, 3 μm or less, sheet attack and defective peeling of the green sheet are suppressed.

[Multilayer ceramic capacitor]
Hereinafter, an example of the multilayer ceramic capacitor and the manufacturing method thereof according to the present embodiment will be described with reference to FIG. In the drawings, they may be schematically expressed as appropriate, or may be expressed by changing the scale.

  FIG. 3 is a cross-sectional view showing an example of the multilayer ceramic capacitor 1 of the present embodiment. The multilayer ceramic capacitor 1 includes a multilayer body 10 in which dielectric layers 12 and internal electrode layers 11 are alternately stacked, and external electrodes 20. The manufacturing process of the multilayer ceramic capacitor 1 is as follows. First, a plurality of dielectric layers 12 made of ceramic green sheets and a plurality of internal electrode layers 11 formed of the above-mentioned internal electrode paste are alternately laminated by pressure bonding. After obtaining the laminated body 10, the laminated body 10 is fired and integrated to produce a laminated ceramic fired body that becomes a multilayer ceramic capacitor body. Then, the multilayer ceramic capacitor 1 is manufactured by forming a pair of external electrodes 20 at both ends of the ceramic capacitor body.

  First, a ceramic green sheet that is an unfired ceramic sheet is prepared. As this ceramic green sheet, for example, a dielectric layer paste obtained by adding an organic binder such as polyvinyl butyral and a solvent such as terpineol to a predetermined ceramic raw material powder such as barium titanate, a PET film or the like. Examples thereof include a sheet formed on a support film and dried to remove the solvent. The thickness of the dielectric layer 12 formed from the ceramic green sheet is not particularly limited, but is preferably 0.05 μm or more and 3 μm or less from the viewpoint of demand for downsizing of the multilayer ceramic capacitor.

  Next, the internal electrode layer 11 formed from the internal electrode paste is printed on one side of the ceramic green sheet by printing and applying the internal electrode paste described above by a known method such as a screen printing method. Prepare a plurality of the formed ones. In addition, it is preferable that the thickness of the internal electrode layer 11 formed from the internal electrode paste is 1 μm or less from the viewpoint of a request for thinning the internal electrode layer 11.

  Next, the ceramic green sheets are peeled from the support film, and the dielectric layers 12 formed from the ceramic green sheets and the internal electrode layers 11 formed from the internal electrode paste formed on one surface thereof are alternately arranged. Thus, the laminated body 10 is obtained by laminating by heating / pressurizing treatment. In addition, it is good also as a structure which arrange | positions the ceramic green sheet for protection which does not apply | coat the paste for internal electrodes on both surfaces of the laminated body 10. FIG.

Next, after the laminated body 10 is cut into a predetermined size to form a green chip, the green chip is subjected to a binder removal treatment and fired in a reducing atmosphere to produce a laminated ceramic fired body. The atmosphere in the debinding process is preferably air or N ₂ gas atmosphere. The temperature at which the binder removal treatment is performed is, for example, 200 ° C. or higher and 400 ° C. or lower. Moreover, it is preferable that the holding time of the said temperature at the time of performing a binder removal process shall be 0.5 hours or more and 24 hours or less. The firing is performed in a reducing atmosphere in order to suppress oxidation of the metal used for the internal electrode layer 11, and the temperature at which the laminate 10 is fired is, for example, 1000 ° C. or higher and 1350 ° C. or lower, The temperature holding time when firing is, for example, not less than 0.5 hours and not more than 8 hours.

  By firing the green chip, the organic binder in the green chip is removed and the ceramic raw material powder is fired to form the ceramic dielectric layer 12. Further, the organic vehicle in the internal electrode layer 11 is removed, and the conductive powder is sintered or melted and integrated to form an internal electrode, and a plurality of dielectric layers 12 and internal electrode layers 11 are alternately formed. A multilayer ceramic fired body laminated on is formed. In addition, annealing may be performed on the fired green chip from the viewpoint of taking oxygen into the dielectric layer to enhance electrical characteristics and suppressing reoxidation of the internal electrode.

  Then, a multilayer ceramic capacitor 1 is manufactured by providing a pair of external electrodes 20 to the manufactured multilayer ceramic fired body. For example, the external electrode 20 includes an external electrode layer 21 and a plating layer 22. The external electrode layer 21 is electrically connected to the internal electrode layer 11. The external electrode 20 may include a layer other than the external electrode layer 21 and the plating layer 22. Further, the external electrode 20 may not include the plating layer 22. As a material of the external electrode 20 (external electrode layer 21, plating layer 22), for example, copper, nickel, or an alloy thereof can be preferably used.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

[Example 1]
(Preparation of organic vehicle)
The organic vehicle preparation includes a step (i) of preparing a first organic vehicle containing polyvinyl butyral resin (PVB) and a step (ii) of preparing a second organic vehicle containing ethyl cellulose (EC), respectively. Carried out.
(I) First organic vehicle preparation step First, about 65 parts by mass of terpineol (α, β, γ mixture) as the first organic solvent, half of the addition amount (32.5 parts by mass) is heated to 60 ° C. did. Then, while stirring the heated terpineol with an impeller (impeller), 2.4 parts by mass of polyvinyl butyral was gradually added to prepare a first organic vehicle containing a polyvinyl butyral resin.
(Ii) Second Organic Vehicle Preparation Step Similarly, in the second organic vehicle preparation step, about 65 parts by mass of organic solvent terpineol (α, β, γ mixture) is half the amount added (32.5 Part by weight) was heated to 60 ° C. Then, while stirring the heated terpineol with an impeller (impeller), 3.4 parts by mass of ethyl cellulose resin was gradually added to prepare a second organic vehicle containing ethyl cellulose.

(Dispersion process)
Nickel powder (average particle size: 0.4 μm), which is a conductive powder, was prepared in an amount such that the content in the internal electrode paste was 48.3 mass% (100 mass parts). 70.8 parts by mass of two kinds of organic vehicles (first organic vehicle and second organic vehicle) prepared in the organic vehicle preparation step and BaTiO ₃ (average particle diameter) as ceramic powder with respect to 100 parts by mass of nickel powder : 0.1 μm) 15.0 parts by mass, oleic acid 1.0 parts by mass as an anionic surfactant, saturated aliphatic hydrocarbon solvent (No. 0 Solvent (trade name) as second organic solvent: After adding 20.0 parts by mass of JX Nippon Mining & Energy Corporation, ethylene glycol (manufactured by Kanto Chemical Co., Inc., boiling point: 198 ° C.) as the same amount as the molar amount of COOH groups contained in oleic acid, these The mixture was stirred and mixed with a mixer to obtain a slurry. The obtained slurry was further completely dispersed using a three-roll mill to produce an internal electrode paste. Table 1 shows the mixing ratio of the components used.

  In addition, the No. 0 solvent (manufactured by JX Nippon Oil & Energy Corporation) contains 99 vol% or more of saturated hydrocarbons, and contains tridecane, nonane, and cyclohexane as main components.

[viscosity]
The paste immediately after the production was measured with a viscometer manufactured by Brookfield, and the viscosity at 10 rpm was measured, and a value of 20 to 60 Pa · s was evaluated as ◯ (good), and the other was evaluated as x (bad).
[Dry film density]
The film was applied at 250 μm, dried at 120 ° C. for 60 minutes, cut out at 4 cmφ, measured for weight and thickness, and the dry film density was calculated. A film having a dry film density of 5 g / cm ³ or more was evaluated as ◯ (good), and a film density lower than that was evaluated as x (defective).
[Adhesion evaluation]
The prepared paste was printed on a 4 μm thick green sheet (containing BaTiO ₃ and polyvinyl butyral resin) and dried at 80 ° C. for 3 minutes or 10 minutes. Thereafter, the sheet on which the internal electrode paste was printed was heated to 50 ° C., and a laminate (internal electrode layer thickness: 1 μm) composed of 50 layers was produced while applying a pressure of 10 MPa. The laminated body was cut and collected, and the adhesion of each layer was observed with an optical microscope. When the drying time is 3 minutes, the evaluation in which 50 layers were not peeled between layers was evaluated as ◎ (very good), and when the drying time was 10 minutes, the separation between layers was observed in 50 layers. Those that were not seen were evaluated as “good” and “good”, and even when the drying time was 3 minutes and 10 minutes, the case where peeling between layers was seen in 50 layers was judged as “poor”. .

[Evaluation of gelation inhibition]
Evaluation of gelation suppression was performed by calculating the rate of change in viscosity after the prepared paste was allowed to stand for a certain period. When the paste is gelled, the paste viscosity greatly increases. The viscosity of the paste was measured immediately after production of the paste and after standing for 90 days at room temperature (25 ° C.) using a Brookfield B-type viscometer under a condition of 10 rpm (shear rate = 4 sec ⁻¹ ). It was calculated using the following formula (2). When the viscosity change rate was ± 30%, it was evaluated as ×, when it was ± 15%, Δ, and when it was ± 10%, it was evaluated as ○.
Viscosity change rate (%) = [(viscosity after standing for 90 days−viscosity immediately after production) / viscosity immediately after production] × 100) (2)
Table 1 shows the evaluation results.

[Example 2]
An internal electrode paste was prepared in the same manner as in Example 1 except that the amount of glycol added was 2 mol times the mol amount of COOH groups contained in oleic acid.
[Example 3]
An internal electrode paste was prepared in the same manner as in Example 1 except that the amount of oleic acid added was 5 times that in Example 1.
[Example 4]
An internal electrode paste was prepared in the same manner as in Example 3 except that the amount of glycol added was 2 mol times the mol amount of COOH groups contained in oleic acid.
[Example 5]
An internal electrode paste was prepared in the same manner as in Example 1 except that the amount of oleic acid added was 6 parts by mass.
[Example 6]
An internal electrode paste was produced in the same manner as in Example 5 except that the amount of glycol added was 2 mol times the mol amount of COOH groups contained in oleic acid.
[Example 7]
An internal electrode paste was prepared in the same manner as in Example 3 except that stearic acid (carbon number: 18) was used as the anionic surfactant.
[Example 8]
Internal electrode in the same manner as in Example 3 except that the ratio [(polyvinyl butyral content) / (ethyl cellulose content)] of the organic binder in the organic vehicle was changed to [4.8 parts by mass / 1 part by mass]. A paste was prepared.
[Example 9]
In the dispersion step, instead of 20 parts by mass of a saturated aliphatic hydrocarbon solvent (second organic solvent), 24 parts by mass of terpineol (first organic solvent) was used, and propylene glycol (manufactured by Kanto Chemical Co., Inc., boiling point) The internal electrode paste was prepared in the same manner as in Example 3 except that 188 ° C. was used.

[Example 10]
An internal electrode paste was prepared in the same manner as Example 9 except that diethylene glycol (manufactured by Kanto Chemical Co., Inc., boiling point: 245 ° C.) was used as the glycol.
[Example 11]
An internal electrode paste was prepared in the same manner as in Example 9 except that triethylene glycol (manufactured by Kanto Chemical Co., Inc., boiling point: 288 ° C.) was used as the glycol.
[Example 12]
An internal electrode paste was prepared in the same manner as in Example 9 except that tetraethylene glycol (manufactured by Kanto Chemical Co., Inc., boiling point: 327 ° C.) was used as the glycol.

[Comparative Examples 1, 2, 3]
The amount of glycol added was changed as shown in Table 1 (Comparative Example 1: No addition of glycol, Comparative Example 2: 0.5 mol times with respect to COOH groups, Comparative Example 3: 3 mol times with respect to COOH groups) In the same manner as in Example 1, an internal electrode paste was prepared.
[Comparative Example 4]
An internal electrode paste was prepared in the same manner as in Example 5 except that no glycol was added.

  Table 1 shows the compositions and evaluation results of the internal electrode pastes used in the above Examples and Comparative Examples.

[Evaluation results]
The internal electrode paste produced in the examples had good viscosity, dry film density, and adhesion. In addition, gelation of the internal electrode paste to which 0.5% by mass or more of glycol was added was suppressed even after long-term storage.
On the other hand, in Comparative Examples 1 and 2 in which no glycol was added or the addition amount was small, the viscosity and the dry film density were good, but the adhesion was not improved. In Comparative Example 3, since the amount of glycol added was too large, the paste viscosity was greatly reduced and it was difficult to actually use it. In Comparative Example 4 in which the addition amount of the anionic surfactant was increased without adding the glycol, the viscosity, the dry film density and the adhesion were poor. The paste of Comparative Example 4 is considered to have poor adhesion because the carboxyl group of oleic acid hindered hydrogen bonding between the internal electrode layer and the polyvinyl butyral resin in the dielectric layer.

  The internal electrode paste of the present invention is very excellent in adhesion, and the occurrence of peeling and misalignment between internal electrode layers is extremely suppressed. Especially, chip parts for electronic devices such as mobile phones and digital devices. It can be suitably used as a raw material for the internal electrode of the multilayer ceramic capacitor.

DESCRIPTION OF SYMBOLS 1 Multilayer ceramic capacitor 10 Laminated body 11 Internal electrode layer 12 Dielectric layer 20 External electrode 21 External electrode layer 22 Plating layer

Claims (10)

An internal electrode paste containing conductive powder, ceramic powder, ethyl cellulose resin, polyvinyl butyral resin, organic solvent and anionic surfactant,
The polyvinyl butyral resin is contained in an amount of 1% by mass to 2.5% by mass with respect to the total amount of the paste,
The anionic surfactant has at least one carboxyl group (COOH group) and is contained in an amount of 0.1 parts by mass or more and 6.5 parts by mass or less with respect to 100 parts by mass of the conductive powder.
The paste for internal electrodes which contains glycol in the range of more than 0.5 mol times and less than 3 mol times with respect to the carboxyl group (COOH group) which the said anionic surfactant has.   The internal electrode paste according to claim 1, wherein the glycol has a boiling point of 300 ° C. or less.   The internal electrode paste according to claim 1 or 2, wherein the glycol is at least one selected from ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol.   The internal electrode paste according to any one of claims 1 to 3, wherein the conductive powder has an average particle size of 0.05 µm or more and 0.5 µm or less.   The internal electrode paste according to any one of claims 1 to 4, wherein the anionic surfactant has 16 to 22 carbon atoms.   6. The internal electrode according to claim 1, wherein the organic solvent includes a first organic solvent and a second organic solvent having a boiling point lower than that of the first organic solvent. paste.   The internal electrode paste according to claim 6, wherein the first organic solvent has a boiling point of 150 ° C. or higher and 300 ° C. or lower, and the second organic solvent has a boiling point of 120 ° C. or higher and 250 ° C. or lower.   The glycol is contained in a range of 0.5% by mass or more with respect to 100% by mass of the total amount of conductive powder, ceramic powder, organic binder, and organic solvent. Internal electrode paste. Preparing an organic vehicle by mixing with an organic binder and an organic solvent;
Adding and dispersing conductive powder, ceramic powder, an anionic surfactant, and glycol in the organic vehicle,
The anionic surfactant has at least one carboxyl group (COOH group) and is added in a range of 0.1 parts by mass to 6.5 parts by mass with respect to 100 parts by mass of the conductive powder. And
The method for producing an internal electrode paste, wherein the glycol is added in a range of more than 0.5 mol and less than 3 mol with respect to the carboxyl group (COOH group) of the anionic surfactant.   It is a multilayer ceramic capacitor provided with the laminated body on which the dielectric material layer and the internal electrode layer were laminated | stacked alternately, Comprising: The said internal electrode uses the paste for internal electrodes as described in any one of Claims 1-8. Multilayer ceramic capacitor formed by

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