JP6732250B2 - Method of manufacturing intermediate product of ceramic electronic component, intermediate product of ceramic electronic component and ceramic electronic component - Google Patents

Description

The present invention relates to a method for manufacturing an intermediate product of a ceramics electronic component such as a laminated ceramics capacitor, and in particular, an internal electrode is exposed by etching a ceramics electronic component body in which the periphery of the electronic component including the internal electrode is covered with ceramics. Thus, the present invention relates to a method for manufacturing an intermediate product of a ceramic electronic component for obtaining the intermediate product.

For example, in a laminated ceramic capacitor, which is one of the ceramic electronic components, a plurality of ceramic layers and internal electrodes are alternately laminated, and the laminated body is pressure-bonded and cut to obtain a green chip, that is, an element body for a laminated ceramic capacitor. Thereafter, the element body for a laminated ceramic capacitor is fired, and then external electrodes are formed on both end surfaces of the element body for a laminated ceramic capacitor after the firing (for example, Patent Document 1 and Patent Document 2). reference).

Hereinafter, in the present invention, an element body for a laminated ceramic capacitor and an element body for a laminated ceramic capacitor obtained by firing the element body are referred to as an intermediate product of the laminated ceramic capacitor and an intermediate product of the laminated ceramic capacitor after firing, respectively.

Manufacture of such a multilayer ceramic capacitor is performed through the following steps.
First, as shown in FIG. 120(a), a plurality of ceramic layers 2 and internal electrodes 3 are alternately laminated, and the laminated body is pressure-bonded and cut to obtain an intermediate product 4 of a laminated ceramic capacitor. In the intermediate product 4 of the multilayer ceramic capacitor before firing, as shown in FIG. 120(a), the end face of the internal electrode 3 is exposed outward from the end face of the ceramic layer 2, but when this is fired, As shown in FIG. 120( b ), the internal electrode 3 is buried in the ceramic layer 2 due to the difference in thermal expansion coefficient and thermal contraction coefficient between the ceramic layer 2 and the internal electrode layer 3. Therefore, at least an end portion of the intermediate product 40 of the laminated ceramic capacitor after firing is physically polished and removed, and the end surface of the internal electrode 3 is exposed outward from the end surface of the ceramic layer 2 to obtain the intermediate product 100 of the laminated ceramic capacitor. After obtaining (see FIG. 120(c)), the external electrodes 5 and 5 are provided on both ends of the intermediate product 100 (see FIG. 120(d)). The laminated ceramic capacitor 110 is manufactured through this process.

By the way, when the end portion of the ceramic body (the intermediate product 40 of the laminated ceramic capacitor after firing) is physically polished and removed to expose the end surface of the internal electrode 3 outward from the end surface of the ceramic layer 2, water is removed. Japanese Patent Application Laid-Open No. 2004-242242 discloses that an aqueous solution in which a complexing agent is dissolved, a ceramic body and an abrasive are placed in a polishing tank to polish the ceramic body.

Further, in Patent Document 1, the complexing agent causes a solubilizing action in which polishing powder or polishing dust, which is difficult to dissolve in water, is diffused in water, thereby causing a state change in water. It is disclosed that due to such a change in the state of water, diffused polishing powder or polishing debris prevents water from entering the gap between the ceramic layer and the internal electrode.

In such a method for producing a multilayer ceramic electronic component, the complexing agent has a composition formula represented by C ₆ H ₁₁ O ₇ M, and M is a gluconate selected from Na, K, Mg, and Ca. As the complexing agent, a citrate whose composition formula contains C ₆ H ₈ O ₇ can be used (see Patent Document 1). It is described that a carboxylic acid-based complexing agent can be used to cause a state change in water, and in particular, the gluconate or citrate as described above can be used (Patent Reference 1).

JP, 2014-212233, A JP, 2007-208112, A Japanese Patent Application No. 2015-007236

However, when manufacturing a laminated ceramic capacitor by the conventional method, the end portion of the ceramic layer 2 in the intermediate product 40 of the laminated ceramic capacitor after firing is physically polished and removed to expose the end surface of the internal electrode 3. Therefore, since the external electrode 5 is provided, it is necessary to select a polishing tip according to the size of the intermediate product 40, and the work is complicated and troublesome, and special special equipment is required. Has occurred. In particular, when the monolithic ceramic capacitor is small and is composed of an extremely large number of laminates of the ceramic layers 2 and the internal electrodes 3, defective products are likely to occur, which causes problems such as deterioration in yield and quality.

Further, since the end surface of the intermediate product 40 of the laminated ceramic capacitor is physically polished by a dedicated jig such as shot blasting or barrel polishing, the polishing surface is roughened or the end portion of the ceramic layer 40 is polished. At this time, a damaged portion 3a may occur at the end of the internal electrode 3, or the scrap 2b may adhere to the end surface of the intermediate product 40, resulting in poor contact between the internal electrode 3 and the external electrode 5. As a result, the external electrode 5 cannot be provided firmly and surely in close contact with the internal electrode 3. Moreover, the abrasive used here is extremely small, which makes it extremely difficult to separate the intermediate product 40 and the abrasive after the polishing.
As a result, there arise problems such as deterioration of quality, variation in quality, and deterioration of workability.

Further, if the end portion of the intermediate product 40 after polishing is physically polished, the dedicated jig will be consumed. Therefore, unless the polishing is frequently performed while confirming the consumption state, the processing accuracy will decrease and the accuracy will decrease. Problems such as generation of non-defective products also occur.

In addition, when physically polishing the end of the intermediate product 40 after polishing, the impact may damage the laminated structure of the intermediate product 40 or damage the electrodes, thereby deteriorating the dielectric characteristics. Will also occur.

On the other hand, Patent Document 1 discloses or suggests that the complexing agent causes polishing powder or polishing dust diffused in water to enter the gap between the ceramic layer and the internal electrode to prevent water from entering the gap. In this way, it is disclosed that it is possible to prevent water from entering the ceramic element body, prevent water from expanding due to heat when the external electrode is formed, and prevent cracks from occurring in the ceramic element body. ing.

That is, in Patent Document 1, it is possible to prevent the occurrence of cracks in the ceramic element body (the intermediate product 40 of the laminated ceramic capacitor after firing), but the above-mentioned adverse effects caused by physically polishing the ceramic element body are solved. It is judged that they cannot do it.

By the way, the inventors of the present invention have found that sodium fluoride, sodium acid fluoride, potassium fluoride, potassium acid fluoride, ammonium acid fluoride, neutral ammonium fluoride, sodium chloride, potassium chloride, ammonium chloride, sodium bromide. , The end portion of the ceramic layer is etched by using a treatment aqueous solution containing at least one halogen compound (etching agent) selected from potassium bromide or ammonium bromide, and the ceramic layer is buried in the ceramic layer. Japanese Patent Application No. 2005-007236 (see Patent Document 3) proposes a method of exposing the end surface or the end portion of the internal electrode outward from the end surface of the ceramic layer.

According to this method, the productivity can be remarkably improved, the adhesion between the internal electrode and the external electrode is very good, the reliability is high, and the yield is very good. It is characterized in that it is possible to obtain a stable and stable intermediate product of a monolithic ceramic capacitor.
On the other hand, in the above-described manufacturing method using a treatment aqueous solution containing a halogen-based compound, minute cracks and recesses present in the ceramic layer, a connecting portion between the external electrode and the ceramic chip, etc. (hereinafter, these are collectively referred to as “ If the halogen-based compound (containing a treatment aqueous solution (hereinafter, referred to as an etching agent)) remains in “surface defects and the like”, there is a problem that internal electrodes and electronic parts are corroded with the passage of time. In addition, water (washing liquid in each process) for cleaning, and (moreover, ceramic electronic parts) used in a high humidity environment, etc., moisture (moisture) permeates inside from the surface defects, etc. There is also the problem of corroding electronic components.

The present invention has been made in view of such a problem, and prevents the penetration of an etching agent, a cleaning liquid, moisture (moisture), a plating liquid, and the like into the inside from surface defects and the like, An object of the present invention is to provide an intermediate product of a ceramic electronic component and a manufacturing method capable of obtaining a long-life ceramic electronic component, which prevents corrosion, and an intermediate product of the ceramic electronic component and a ceramic electronic component produced by this method.

In order to solve the above problems, in the method for producing an intermediate product of a ceramic electronic component of the present invention, an etching agent is obtained after obtaining a ceramic electronic component body in which the periphery of the electronic component including internal electrodes is coated with ceramics. A neutralizing agent having the property of reacting with and neutralizing, at least impregnated into the inside from the surface defect or the like of the end portion or end face of the ceramic electronic component body intended to expose the internal electrode, and thereafter, The etching agent is brought into contact with at least the end portion or end surface of the ceramic electronic component element body, whereby the ceramic is etched, and the internal electrodes buried in the ceramic are exposed outward from the ceramic. In addition, the neutralizing agent impregnated inside the surface defects and the like and the etching agent are neutralized.

According to the present invention, by the neutralization reaction of the neutralizing agent and the etching agent impregnated inside the surface defects and the like, the etching agent penetrates from the surface defects and the like to the internal electrodes and electronic parts. The problem of corrosion can be prevented.
After the etching, a step of impregnating a surface defect or the like of the end portion or the end surface of the ceramic electronic component element body in which at least the internal electrodes are exposed with a neutralizing agent having a property of reacting with the etching agent to neutralize May be further provided.
By doing so, even if the etching agent is not completely washed off by the post-etching cleaning, it is possible to prevent a problem that the etching agent permeates into the inside from the surface defects due to the neutralization reaction after the etching. You can
Further, by setting the amount of the neutralizing agent to be impregnated into the surface defects and the like such that the residue remains after the neutralization and solidifies inside the surface defects and the like, the remaining etching agent is removed from the surface defects and the like. When it penetrates into the interior, it is neutralized by the solidified residue, and the solidified residue seals surface defects, etc., so that it is possible to prevent the penetration of cleaning liquid such as water or moisture into the interior. ..

In the present invention, at least an end portion or an end surface of the ceramic electronic component body is immersed in a treatment aqueous solution containing an etching agent or a neutralizing solution containing the neutralizing agent, or in the ceramic electronic component body. By coating or spraying or spraying the treatment aqueous solution or the neutralizing solution on at least the end portion or the end surface, the treatment aqueous solution is brought into contact with at least the end portion or the end surface of the ceramic electronic component body or the neutralizing solution is added. It may be impregnated.
Further, the whole body of the ceramic electronic component body is impregnated with the neutralizing agent, and the neutralizing agent impregnated in the whole body of the ceramic electronic component is neutralized by the etching agent. Good.
By adjusting at least one of the concentration, temperature or pressure of the neutralizing agent or the contact time between the neutralizing agent and the ceramic electronic component body, the neutralization is performed inside the surface defects and the like. The agent may be impregnated.
The etching agent is a halogen-based compound, such as sodium fluoride, sodium acid fluoride, potassium fluoride, potassium acid fluoride, ammonium acid fluoride, neutral ammonium fluoride, sodium chloride, potassium chloride, ammonium chloride, and odor. At least one selected from sodium bromide, potassium bromide, and ammonium bromide can be used.
The concentration of the treatment aqueous solution containing the halogen-based compound is preferably 0.001 to 10.0% by weight.

Examples of the neutralizing agent include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkaline earth metal hydroxides such as calcium hydroxide. It is preferable to use at least one selected from the above.
In the present invention, the term “contact” means that a treatment aqueous solution containing a halogen-based compound of the present invention, which will be described later, comes into contact with an end or the whole of an intermediate product of a ceramic electronic component. There is no particular limitation as long as the treatment aqueous solution containing the system compound can touch at least the end of the intermediate product of the ceramic electronic component. Specifically, it means, for example, immersing the end or the whole of the intermediate product in the treatment aqueous solution, or applying, spraying or spraying the treatment aqueous solution on the end or the whole of the intermediate product.

Further, in the present invention, "etching" means eroding the joint between the ceramic particles at the end of the intermediate product of the ceramic electronic component, or penetrating between the ceramic particles at the end of the intermediate product and Peeling and release between the two, and further dispersing the ceramic particles in a treatment aqueous solution containing a halogen-based compound. In this case, it is desirable to perform ultrasonic treatment in order to more effectively separate and separate the ceramic particles and further disperse the ceramic particles in the treatment aqueous solution.

By such a method, the end surface or the end portion of the internal electrode buried in the ceramic layer in the intermediate product of the ceramic electronic component after firing can be exposed outward from the end surface of the ceramic layer.

In the method for producing an intermediate product of a ceramic electronic component according to the present invention, internal electrodes are printed/baked with a conductive paste containing metal powder, and an inkjet method is used in which conductive ink containing metal powder is atomized and ejected from a nozzle. It is preferable to use one formed by baking, spraying/baking a conductive paste containing metal powder, or vapor deposition, plating or sputtering of metal.

In the method for producing an intermediate product of a ceramic electronic component of the present invention, at least the end portion of the intermediate product of the ceramic electronic component and the contact time of the treatment aqueous solution containing a halogen-based compound, the temperature of the treatment aqueous solution, or the temperature of the treatment aqueous solution. By adjusting any one or more of the concentrations of the halogen-based compound, the oxide film generated during firing is removed from the end surface of the internal electrode, the end surface is activated, and the end of the internal electrode is removed. It is desirable to remove the end portion of the ceramic layer covering the portion.

In the method for producing an intermediate product of a ceramic electronic component of the present invention, at least the end portion of the intermediate product of the ceramic electronic component and the contact time of the treatment aqueous solution containing a halogen-based compound, the temperature of the treatment aqueous solution, or the temperature of the treatment aqueous solution. The end surface or end of the internal electrode is exposed or protruded outward within a range of 1 to 2.5 μm flush with the end surface of the ceramic layer by adjusting one or more of the concentrations of the halogen-based compound. Is desirable.

In the method for producing an intermediate product of a ceramic electronic component of the present invention, at least the end portion of the intermediate product of the ceramic electronic component and the contact time of the treatment aqueous solution containing a halogen-based compound, the temperature of the treatment aqueous solution, or the temperature of the treatment aqueous solution. By adjusting any one or more of the concentrations of the halogen-based compound, a porous portion composed of pores or porous portions is formed at the end of the ceramic layer within the depth of 3 μm from the end face of the ceramic layer. It is desirable that it has been done.

The treatment aqueous solution containing a halogen-based compound used in the present invention preferably contains an etching accelerator for promoting etching.

In the treatment aqueous solution containing the halogen compound used in the present invention, the etching accelerator is selected from hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, hypochlorous acid, phosphoric acid, boric acid, polyphosphoric acid or polyboric acid. At least one or more inorganic acids or their alkali metal salts or ammonium salts are desirable.

In the treatment aqueous solution used in the present invention, it is desirable that a surface stabilizer for stabilizing the activated surface of the intermediate product of the ceramic electronic component after etching is added to the intermediate product.

In the treatment aqueous solution used in the present invention, the surface stabilizer is preferably a protective film-forming substance consisting of at least one organic acid selected from oxycarboxylic acids or dicarboxylic acids or their alkali metal salts or ammonium salts. ..

In the treatment aqueous solution used in the present invention, the protective film forming substance is gallic acid, pyrogallol, citric acid, malic acid, lactic acid, tartaric acid, glycolic acid, glyceric acid, tannic acid, oxyvaleric acid, salicylic acid, mandelic acid, Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid or fumaric acid or their alkali metal salts or ammonium salts, or at least one selected from the alkali metal salts or ammonium salts of EDTA Is desirable.

The intermediate product of the ceramic electronic component of the present invention is an intermediate product of the ceramic electronic component in which the internal electrode is exposed by an etching agent from the ceramic electronic component element body in which the periphery of the electronic component including the internal electrode is coated with ceramics. , A neutralizing agent having a property of reacting with an etching agent impregnated in the inside from a surface defect or the like of an end portion or an end surface of the ceramic electronic component body to be neutralized and solidified by reacting with the etching agent Further, the residue of the neutralizing agent is filled inside the surface defects and the like .
The ceramics electronic component of the present invention includes a ceramics electronic component body whose periphery is covered with ceramics, internal electrodes exposed from the ceramics electronic component body by an etching agent, and both ends of the ceramics electronic component body. External electrodes electrically connected to the internal electrodes at a plurality of parts or side surfaces, and filled inside the surface defects of the ceramic electronic component body exposing the internal electrodes, and the etching agent. It has a neutralizing agent having a property of reacting and neutralizing, and a residue of the neutralizing agent produced by the neutralization of the etching agent and solidified .

The manufacturing method of the ceramic electronic component obtained by the manufacturing method of the present invention, in the intermediate product of the ceramic electronic component, external electrodes are formed at both ends or at a plurality of locations on the side surface so as to be electrically connected to the internal electrodes. It is desirable that

In the production of the ceramics electronic component obtained by the production method of the present invention, the external electrodes are coated/baked with a conductive paste, dipping/baked with a conductive paste, printed/baked with a conductive paste, and conductive containing a metal powder. Desirably, the ink is formed by printing/baking by an inkjet method in which the ink is atomized and ejected from a nozzle, spraying/baking a conductive paste containing a metal powder, or vapor deposition, plating or sputtering of a metal.

As described above, in the method for producing an intermediate product of a ceramic electronic component processed by chemical polishing, it is possible to remarkably improve the productivity of the intermediate product of the ceramic electronic component and the ceramic electronic component. It is possible to obtain the intermediate product or the ceramic electronic component, which has excellent adhesion to external electrodes, high reliability, and extremely high yield, and high quality such as electric characteristics and stable.
In the method of manufacturing an intermediate product of a ceramic electronic component by such effective chemical polishing, corrosion of internal electrodes and electronic components is prevented by preventing moisture such as an etching agent and a cleaning liquid from penetrating inside due to surface defects and the like. And an intermediate product of a long-life ceramic electronic component can be obtained.

In FIG. 1, (a) is a schematic cross-sectional view of an intermediate product of a laminated ceramic capacitor before firing and its partially enlarged cross-sectional view, and (b) is a schematic cross-sectional view of an intermediate product of a laminated ceramic capacitor after firing and its partially enlarged cross-section. FIG. 6(c) is a schematic cross-sectional view of an intermediate product of the multilayer ceramic capacitor of the present invention obtained by performing the treatment according to the present invention and a partially enlarged cross-sectional view thereof, and (d) is the book obtained in the above (c). FIG. 1 is a schematic cross-sectional view and a partially enlarged cross-sectional view of a laminated ceramic capacitor of the present invention obtained by attaching external electrodes to an intermediate product of the laminated ceramic capacitor of the present invention. It is a partially broken schematic sectional view showing a multilayer ceramic capacitor (ceramic electronic component) according to the present invention. It is a schematic diagram which shows the manufacturing process of the intermediate product of a laminated ceramic capacitor (ceramic electronic component). It is a flow chart explaining the manufacturing method of the intermediate product of the ceramics electronic parts of the present invention. 3 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 1. 5 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 2. 5 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 3. 5 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 4. 8 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 5. 7 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 6. 9 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 7. 9 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 8. 11 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 9. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 10. 16 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 11. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 12. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 13. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 14. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 15. 16 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 16. 20 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 17. 20 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 18. 20 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 19. 20 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 20. 22 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 21. 23 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 22. 23 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 23. 20 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 24. 28 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 25. 27 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 26. 28 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 27. 28 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 28. 32 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 29. 32 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 30. 32 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 31. 33 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 32. 33 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 33. 34 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 34. 36 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 35. 37 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 36. 38 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 37. 38 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 38. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 39. 32 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 40. 38 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 41. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 42. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 43. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 44. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 45. 17 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 46. 38 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 47. 38 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 48. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 49. 20 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 50. 20 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 51. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 52. 34 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 53. 28 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 54. 38 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 55. 28 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 56. 28 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 57. 28 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 58. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 59. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 60. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 61. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 62. 38 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 63. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 64. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 65. 37 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 66. 28 is an electron micrograph of an intermediate product of a laminated ceramic capacitor (ceramic electronic component) according to Example 67. 28 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 68. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 69. 20 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 70. 20 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 71. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 72. 38 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 73. 17 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 74. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 75. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 76. 38 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 77. 38 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 78. 38 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 79. 32 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 80. 38 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 81. 38 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 82. 38 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 83. 38 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 84. 38 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 85. 38 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 86. 38 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 87. 38 is an electron micrograph of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) according to Example 88. 20 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 89. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 90. 9 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 91. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 92. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 93. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 94. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 95. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 96. 9 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 97. 9 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 98. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 99. 5 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 100. 5 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 101. 5 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 102. 5 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 103. 8 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 104. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 105. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 106. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 107. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 108. 9 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 109. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 110. 11 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 111. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 112. 16 is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to Example 113. 3 is an electron micrograph showing an intermediate product of a laminated ceramic capacitor (ceramic electronic component) after firing, which is not yet treated with the aqueous treatment solution of the halogen-based compound according to the present invention. FIG. 119A is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to the first embodiment of the method for manufacturing an intermediate product of a multilayer ceramic capacitor. FIG. 119B is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) according to the second embodiment of the method for manufacturing an intermediate product of a multilayer ceramic capacitor. In FIG. 120, (a) is a schematic sectional view of an intermediate product of a laminated ceramic capacitor (ceramic electronic component) before firing and a partially enlarged sectional view thereof, and (b) is a laminated ceramic capacitor after firing (ceramic electronic component, hereinafter). Is a schematic cross-sectional view of an intermediate product and a partially enlarged cross-sectional view thereof, and (c) is a schematic cross-sectional view of an intermediate product of the multilayer ceramic capacitor (ceramic electronic component) of the present invention obtained by carrying out the present invention and a partial enlarged view thereof. A sectional view, (d) is a laminated ceramic capacitor (ceramic electronic component) of the present invention obtained by attaching external electrodes to an intermediate product of the laminated ceramic capacitor (ceramic electronic component) of the present invention obtained in (c) above. It is a schematic cross section and its partial expanded sectional view.

Hereinafter, an embodiment according to the present invention will be described based on the drawings, but the present invention is not limited to this embodiment.

FIG. 1 shows an intermediate product 1 of a multilayer ceramic capacitor (ceramic electronic component) according to the present invention, and a schematic manufacturing process diagram of a multilayer ceramic capacitor 10 of the present invention obtained by using the intermediate product 1, and FIG. The partially fractured schematic sectional view of the multilayer ceramic capacitor 10 of the invention is shown.

The intermediate product 1 of the laminated ceramic capacitor according to the present invention shown in FIG. 1 and the laminated ceramic capacitor 10 according to the present invention are manufactured by the following method.

First, as shown in FIG. 1(a), a plurality of ceramic layers 2 and internal electrodes 3 are alternately laminated, and the laminated body is pressure-bonded and then cut into a predetermined size to obtain an intermediate product 4 of a laminated ceramic capacitor. To manufacture. In this case, when a plurality of the ceramic layers 2 and the internal electrodes 3 are alternately laminated, the end faces of the internal electrodes 3 are alternately exposed to the outside on the both end faces of the intermediate product 4 through the ceramic layers 2. The internal electrodes 3 are laminated and formed so as to be in this state.

Next, the intermediate product 4 is fired to manufacture an intermediate product 40 of the laminated ceramic capacitor after firing. As a result, the intermediate product 40 of the laminated ceramic capacitor after firing is processed into the internal electrode 3 as shown in FIG. The end surface or the end portion of the ceramic layer 2 is buried in the ceramic layer 2 due to the difference in the thermal contraction rate between the ceramic layer 2 and the internal electrode 3, and the contact between the internal electrode 3 and the external electrode 5 described later deteriorates. ..

Therefore, in the present invention, at least an end portion of the intermediate product 40 is etched by bringing it into contact with a treatment aqueous solution containing a halogen-based compound of the present invention, which will be described later, and as a result, as shown in FIG. The end face or the end portion of the internal electrode 3 in the intermediate product 40 is exposed or projected outward from the end face of the ceramic layer 2 to manufacture the intermediate product 1 of the multilayer ceramic capacitor of the present invention.

That is, in the present invention, when at least an end portion of the intermediate product 40 after firing is brought into contact with a treatment aqueous solution containing the halogen-based compound of the present invention, the treatment aqueous solution causes the end portion of the intermediate product 40 to be etched. The erosion of the joint between the ceramic particles, or the separation and release of the ceramic particles at the end of the intermediate product 40, and the separation or release of the ceramic particles dispersed in the treatment aqueous solution. Then, the end face or the end portion of the internal electrode 3 buried in the ceramic layer 2 is exposed or protruded outward from the end face of the ceramic layer 2 to manufacture the intermediate product 1 of the multilayer ceramic capacitor of the present invention. It

Then, as shown in FIG. 1D, the laminated ceramic capacitor 10 of the present invention is formed in the following step on both ends of the intermediate product 1 of the laminated ceramic capacitor of the present invention, for example, by a known method. Manufactured by forming.

As described above, in the present invention, first, the intermediate product 1 of the multilayer ceramic capacitor of the present invention is manufactured, and then the obtained intermediate product 1 is provided with external electrodes, for example, by a known method, Since the monolithic ceramic capacitor 10 is manufactured, the intermediate product 1 of the monolithic ceramic capacitor of the present invention will be mainly described in detail below in order to avoid redundant description, and then the monolithic ceramic capacitor of the present invention will be described. To do.

The intermediate product 1 of the multilayer ceramic capacitor of the present invention is not particularly limited as long as it is a ceramic having a dielectric property. Specifically, it is a ferroelectric product having a high relative dielectric constant but a large loss. The dielectric constant may be as low as about 100 or less, but a paraelectric material having a low loss may be used.

Examples of the intermediate product 1 of the laminated ceramic capacitor of the present invention include those in which a ferroelectric material such as barium titanate is used as the ceramic layer 2 or one in which this ferroelectric material is used as a main component. Also, as the other ceramics layer 2, those using paraelectric materials such as forsterite, aluminum oxide, barium niobate magnesium magnesium oxide, barium titanate neodymium oxide, or those using this paraelectric material as a main component, etc. Are listed.

It should be noted that FIG. 3 shows the manufacturing method of the intermediate product 4 of the multilayer ceramic capacitor in more detail.
That is, the intermediate product 4 of the multilayer ceramic capacitor is manufactured by a method similar to the conventional one. Specifically, for example, dielectric ceramic powder such as barium titanate and a binder solution are sufficiently mixed and dispersed. After preparing a slurry by molding the slurry into a sheet to obtain a dielectric sheet 12, after printing a conductive paste 13 that will become the internal electrodes 3 on the dielectric sheet 12, a green sheet 11 is obtained. A plurality of the green sheets 11 are laminated, pressure-bonded, and the obtained laminated body 110 is cut into a predetermined size. The thus obtained intermediate product 4 of the multilayer ceramic capacitor is fired in the firing furnace 20 to produce the intermediate product 40 of the laminated ceramic capacitor after firing.

In the present invention, in the intermediate product 40 of the multilayer ceramic capacitor, the thickness of each layer and the number of layers are not particularly limited. Specifically, for example, the ceramic layer 2 preferably has a thickness in the range of 0.5 to 50 μm, and the internal electrode 3 has a thickness in the range of 0.01 to 3.5 μm. The thickness is preferably 2 μm or less, and the number of laminated layers is not particularly limited, but examples thereof include those having 10 or more layers and those having more than 1000 layers.

Further, in the present invention, the method of forming the internal electrode is not particularly limited, but specifically, the internal electrode is printed/baked with a conductive paste containing a metal powder, or a conductive ink containing a metal powder is used. Examples include those formed by printing/baking by an ink jet method in which mist is sprayed from a nozzle, spraying/baking of a conductive paste containing metal powder, or vapor deposition, plating or sputtering of metal.

The metal powder used for the conductive paste or the conductive ink that becomes the internal electrodes 3 is a simple metal such as Ag, Pd, Pt, Au, Pb, Sn, Cd, Ti, Zn, Ni, Co or Cu. Examples thereof include metal powder, and metal powder made of an alloy containing at least one selected from the simple metals. These metal powders may be used alone or in combination of two or more. Further, these metal materials can be used for vapor deposition, plating or sputtering.

The metal material of the internal electrodes 3 is preferably one that is not oxidized during firing of the intermediate product 40 of the multilayer ceramic capacitor. For example, a noble metal such as Pt, Pd, Au or Ag-Pd alloy is used. It is desirable to use a base metal such as Ni, Co or Cu because it is expensive. Since such a base metal is oxidized in a high temperature oxidizing atmosphere, it is necessary to perform it in a reducing atmosphere under a low oxygen partial pressure. In this case, since there is a risk that the ceramic layer 2 is reduced and becomes a semiconductor, it is desirable to use the ceramic layer 2 that does not become a semiconductor even if it is fired in a reducing atmosphere under a low oxygen partial pressure. It is desirable to use the dielectric ceramics described in JP-B-61-146111 and JP-A-7-272971.

By the way, in the intermediate product 40 of the laminated ceramic capacitor after firing, as shown in FIG. 1B, the end surface or the end portion of the internal electrode 3 is different due to the difference in the thermal contraction rate between the ceramic layer 2 and the internal electrode 3. It may be buried inside the ceramic layer 2 and the contact with the external electrode 5 described later may be deteriorated.

Therefore, in the present invention, in the intermediate product 40 of the multilayer ceramic capacitor, the end surface or the end portion of the internal electrode 3 buried inside the ceramic layer 2 is exposed or projected outward from the end surface of the ceramic layer 2. At this time, at least an end portion of the intermediate product 40 is coated, sprayed or sprayed with a treatment aqueous solution containing the halogen compound of the present invention, or an end portion or the whole of the intermediate product 40 is treated with the halogen compound. It suffices to immerse it in an aqueous solution. In this way, at least the end portion of the intermediate product 40 of the multilayer ceramic capacitor is brought into contact with the treatment aqueous solution containing the halogen-based compound.

In the present invention, whichever of the contact time between at least the end of the intermediate product 40 of the multilayer ceramic capacitor and the treatment aqueous solution containing the halogen-based compound, the temperature of the treatment aqueous solution, or the concentration of the halogen-based compound in the treatment aqueous solution is used. By adjusting one or more of the ceramics, the end surface of the internal electrode 3 is etched to remove the oxide film generated during firing to activate the surface, and at the same time, the ceramic covering the end of the internal electrode 3 is covered. It is desirable to remove the edges of layer 2.

In the present invention, in contacting at least the end portion of the intermediate product 40 of the multilayer ceramic capacitor with the treatment aqueous solution containing the halogen-based compound, the contact time depends on the temperature of the treatment aqueous solution and the concentration of the halogen-based compound. However, it is generally desirable that the treatment time is in the range of 30 seconds to 100 minutes, preferably in the range of 1 to 75 minutes, particularly preferably in the range of 3 to 60 minutes, and the treatment temperature is generally room temperature to 60°C. , Preferably in the range of 25 to 50° C., particularly preferably in the range of 30 to 45° C. Further, the concentration of the halogen-based compound is 0.001 to 10.0% by weight, preferably Is preferably 0.01 to 5.0% by weight, particularly preferably 0.05 to 3.5% by weight. In this case, in contacting at least an end portion of the intermediate product 40 with the treatment aqueous solution, the treatment aqueous solution is sprayed on at least an end portion of the intermediate product 40 in a range of 30 seconds to 100 minutes as necessary. You just have to spray it.

Thus, by contacting at least the end portion of the intermediate product 40 with the treatment aqueous solution under the conditions described above, the intermediate product 1 of the multilayer ceramic capacitor of the present invention is manufactured as shown in FIG. 1(c). Thus, the technical problem of the present invention can be solved in this way.

Further, in the present invention, when at least the end portion of the intermediate product 40 of the laminated ceramic capacitor is brought into contact with the treatment aqueous solution containing the halogen-based compound, the end surface or the end portion of the internal electrode 3 is flush with the end surface of the ceramic layer 2. It is desirable to expose or project to the outside in the range of 2.5 to 2.5 μm, and in order to form in this way, the contact time, the temperature of the treatment aqueous solution, or the halogen system in the treatment aqueous solution is used in the same manner as the above-mentioned conditions. It is desirable to adjust any one or more of the concentrations of the compounds. In this case, the end portion of the internal electrode 3 is separated from the end surface of the ceramic layer 2 by 0.05 to 5 mm by adjusting the above condition, that is, increasing the contact time with the treatment aqueous solution or controlling the concentration and temperature of the treatment aqueous solution. It is more preferable that the thickness is in the range of 2 μm, and it is particularly preferable that the protrusion is outward in the range of 0.1 to 1.5 μm.

Thus, in the intermediate product 1 of the multilayer ceramic capacitor of the present invention, when the end portions of the internal electrodes 3 are projected outward from the end faces of the ceramic layer 2, the external electrodes 5 are formed at both ends of the intermediate product 1. When this is done, not only does the external electrode 5 make contact with the end surface of the internal electrode 3, but the external electrode 5 makes contact with the entire end of the protruding internal electrode 3 as a result, so that the internal electrode 3 and the external electrode 5 Since the contact area becomes large and the adhesion between the external electrode 5 and the internal electrode 3 becomes strong, the contact between the electrodes 3 and 4 is further improved, so that the conductivity between the electrodes 3 and 4 is further improved. It will improve.

In the present invention, the contact time between at least the end of the intermediate product 40 of the laminated ceramic capacitor after firing and the treatment aqueous solution containing the halogen-based compound, the temperature of the treatment aqueous solution, or the halogen-based compound in the treatment aqueous solution. By adjusting any one or more conditions of the concentration, as shown in FIG. 1C, in the range of 3 μm from the end face of the ceramic layer 2 in the intermediate product 1 of the multilayer ceramic capacitor of the present invention. A porous portion 2a composed of pores and porous portions is formed.

Thus, when the porous portion 2a is formed at the end of the ceramic layer 2 in the intermediate product 1 of the multilayer ceramic capacitor of the present invention, when the external electrode 5 is formed at the end, the metal of the external electrode 5 is formed. The components enter the porous portion 2a and are firmly adhered to the external electrode 5 to be connected to the internal electrode 3.

The treatment aqueous solution containing the halogen-based compound of the present invention is used for treating at least both ends of the intermediate product 1 of the multilayer ceramic capacitor of the present invention. The halogen-based compound in the treatment aqueous solution may be a fluorine-based compound or chlorine. At least one selected from the group-based compounds or bromine-based compounds may be mentioned as the active ingredient, and specific examples of these halogen-based compounds include the above-mentioned ones, and among these, particularly, Fluorine-based compounds are most desirable for efficiently solving the problems of the present invention.

In the present invention, as the fluorine-based compound, at least any one or more selected from sodium fluoride, sodium acid fluoride, potassium fluoride, potassium acid fluoride, ammonium acid fluoride, neutral ammonium fluoride and the like. Can be mentioned.

The treatment aqueous solution containing the halogen-based compound of the present invention effectively exposes or projects the end face or the end portion of the internal electrode 3 from the end face of the intermediate product 40 of the multilayer ceramic capacitor, and effectively removes the oxide film existing on the surface of the intermediate product 40. In order to activate the surface, the treatment aqueous solution preferably contains an etching promoter for promoting etching in addition to the halogen-based compound. ..

As the etching accelerator, at least one inorganic acid selected from hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, hypochlorous acid, phosphoric acid, boric acid, polyphosphoric acid or polyboric acid, or an alkali metal salt thereof. Alternatively, ammonium salts may be mentioned, and in the present invention, the same kind or different kinds of inorganic acids and salts thereof may be used in combination. Examples of these salts include alkali metal salts such as sodium and potassium, and if desired, alkaline earth metal salts such as magnesium and calcium may be used.

The concentration of the inorganic acid or salt thereof is in the range of 0.005 to 10.0% by weight, preferably 0.01 to 5.0% by weight, particularly preferably 0.1 to 3.5% by weight. It is desirable to set the range. If the concentration is too low, less than 0.005% by weight, the desired effect cannot be obtained. On the other hand, if the concentration is more than 10.0% by weight, the ceramic layer 2 is excessively etched or the internal electrode 3 is not dissolved. It is not preferable because it may occur. In this case, when using a plurality of types of inorganic acids or salts thereof, it is desirable that the concentration of the total amount thereof be within the above range.

In the present invention, as described above, two or more kinds of inorganic acids may be mixed and used in the treatment aqueous solution containing the halogen-based compound, and in this case, the total concentration of the mixed acid is based on the whole treatment aqueous solution. If the concentration is less than 10.0% by weight or the concentration of ammonium acid fluoride in the treated aqueous solution is less than 4% by weight, the treated aqueous solution is no longer subject to the Poisonous and Deleterious Substances Control Law, and various transportation and storage of the treated aqueous solution is possible. It is desirable because it can be handled easily as a result of not being subject to legal restrictions.

When the intermediate product 40 of the multilayer ceramic capacitor is treated with the treatment aqueous solution containing the halogen-based compound of the present invention thus prepared, the end portion of the ceramic layer 2 in the intermediate product 40 in contact with the treatment aqueous solution is The end surface or the end portion of the internal electrode 3 which is etched and removed so as to be buried inside the ceramic layer 2 is exposed or protrudes outward, and the oxide film and the inactive film on the processed surface of the intermediate product 40 are removed. Is activated.

Thus, when the intermediate product 40 of the multilayer ceramic capacitor is etched with the treatment aqueous solution, the treated surface of the intermediate product 40 is activated by this treatment, but when exposed to air, an oxide film is immediately formed on the active surface. Therefore, it is necessary to protect and stabilize the active surface of the intermediate product 40.

Therefore, in the treatment aqueous solution containing the halogen-based compound according to the present invention, it is desirable to add a surface stabilizer that protects and stabilizes the activated surface of the intermediate product 40 after etching. The agent acts on the active surface of the intermediate product 40 to form a protective film, and as a result, the protective film stabilizes the active surface and delays the formation of an oxide film by air.

That is, in the present invention, metal ions generated from the intermediate product 40 are present on the active surface of the intermediate product 40 of the multilayer ceramic capacitor activated by etching, and the metal ions and the surface stabilizer are bound to each other. As a result, a protective film is formed on the active surface of the intermediate product 40, and oxidation of the active surface is suppressed by this protective film.

Examples of the surface stabilizer include at least one organic acid selected from oxycarboxylic acids or dicarboxylic acids, or a protective film-forming substance composed of an alkali metal salt or ammonium salt thereof. Examples of the substance include those mentioned above, and among these, it is particularly preferable to use a substance having a cyclic structure such as a phenyl group, and specifically, for example, gallic acid, pyrogallol or tannin or an alkali metal thereof. Most preferred are those selected from salts or ammonium salts.

The concentration of the surface stabilizer is generally in the range of 0.001 to 10% by weight in the treatment aqueous solution, preferably 0.05, for the purpose of forming a stable protective film to improve the quality. It is desirable that the range is from 5 to 5% by weight, particularly preferably from 0.1 to 3.5% by weight.

By the way, in the present invention, the treatment aqueous solution containing a hamgen-based compound may be a treatment aqueous solution containing a one-pack type hamgen-based compound in which a hamgen-based compound and a surface stabilizer coexist, or may include a hamgen-based compound. A two-component type of a treatment aqueous solution and a treatment aqueous solution containing a surface stabilizer is prepared. First, the intermediate product 40 of the multilayer ceramic capacitor is treated with a treatment aqueous solution containing a hamgen compound to form an active surface, and The intermediate product 40 having an active surface may be treated with a treatment aqueous solution containing a surface stabilizer to form a protective film on the active surface. In addition, a treatment aqueous solution containing a hamgen-based compound is put into a treatment tank, the intermediate product 40 of the multilayer ceramic capacitor is immersed in the treatment tank to form an active surface on the intermediate product 40, and then the surface is stabilized in the treatment tank. A protective film may be formed on the active surface by adding an agent.

In the present invention, when the two-liquid type aqueous solution is used, a treatment solution containing the surface stabilizer without adding an inorganic acid is also used, but the treatment solution contains the above-mentioned inorganic acid. The formation of the protective film may be promoted. The concentration of this inorganic acid may be adjusted in the same manner as in the above case.

By the way, in the present invention, a protective film that is stronger than the ceramic layer is formed on the exposed or projected end surface or end portion of the internal electrode 3 in the intermediate product 40 of the multilayer ceramic capacitor. The reason is that a uniform electric double layer is formed between the metal ions generated from the end surface or the end of the internal electrode 3 and the internal electrode 3, and the metal ions and the surface stabilizer (protective film forming substance). This is because the carboxyl groups of 1 are bonded to form a more dense protective film on the exposed surface of the internal electrode 3. That is, although the ceramic layer 2 in the intermediate product 40 of the multilayer ceramic capacitor contains a metal oxide, the metal oxide is reduced to a metal during sintering in a reducing atmosphere, and the metal surface is melted to dissolve the metal. Ions are generated, or metal ions are generated from the surface of the ceramics layer 2, and the metal ions and functional groups on the surface of the ceramics layer 2 (functional groups generated by making the surface of the ceramics layer 2 porous) are stabilized. Although functional groups such as carboxyl groups and hydroxyl groups in the agent (substance for forming a protective film) are bound to form a protective film on the surface of the ceramic layer 2 as well, the active exposed surface of the internal electrode 3 is uniform. As a result of a more dense protective film being formed by such an electric double layer, it becomes difficult for an oxide film to be formed on the entire intermediate product 40 of the multilayer ceramic capacitor.

That is, in the present invention, since the active surface of the intermediate product 1 of the multilayer ceramic capacitor whose surface is activated by etching is stabilized by the protective film, even if it is taken out from the treatment aqueous solution and exposed to air, It does not immediately form an oxide film on its active surface.

Incidentally, in the protective film on the surface of the intermediate product 1 of the multilayer ceramic capacitor of the present invention, the functional groups thereof are bonded toward the ceramic layer 2 side and the internal electrode 3 side, while the organic groups are directed outward. When the surface of the intermediate product 1 is coated with a resin or the intermediate product 1 is molded with a sealing resin, the affinity between these resins and the organic group is extremely high, and the adhesiveness with the intermediate product 1 is extremely high. Since it is high, an extremely excellent sealing effect can be obtained.

By the way, in the present invention, as will be described later, in the intermediate product 1 of the multilayer ceramic capacitor of the present invention, the external electrodes 5 are formed at both ends or at a plurality of positions on the side surfaces thereof to manufacture the multilayer ceramic capacitor of the present invention. However, when the external electrode 5 is formed, the protective film is volatilized and decomposed, or is burned and carbon dioxide gas is generated, so that the conductivity between the internal electrode 3 and the external electrode 5 is adversely affected. There is no such thing.

Furthermore, an organic acid or a surfactant may be added to the treatment aqueous solution containing the halogen-based compound of the present invention.

The “organic acid” is mainly added to prevent the surface portion of the intermediate product 40 of the multilayer ceramic capacitor from being excessively etched. There is no particular limitation as long as it can prevent such an etching. As the organic acid, generally, an organic acid having a carboxyl group (-COOH) in the molecule is preferable, and a monocarboxylic acid, dicarboxylic acid, tricarboxylic acid, polyoxymonocarboxylic acid, polyoxydicarboxylic acid or polyoxytricarboxylic acid is used. Examples thereof include acids, and specific examples include citric acid, glycolic acid, malic acid, gluconic acid, lactic acid, formic acid, acetic acid, propionic acid, butyric acid, tartaric acid, oxalic acid and succinic acid. ..

The amount of these organic acids added is appropriately determined depending on the material of the intermediate product 1 of the target laminated ceramic capacitor, the type and concentration of the inorganic acid used, and is not particularly limited. Generally, it is preferably in the range of 0.005 to 10.0% by weight, and more preferably in the range of 0.01 to 5.0% by weight, based on the entire treatment aqueous solution containing the halogen compound. Is more preferable.

If the amount of the organic acid added is less than 0.005% by weight based on the whole treatment aqueous solution containing the halogen-based compound, the action and effect are insufficient, and the desired suppression effect cannot be obtained, which is not preferable. If the amount exceeds 10.0% by weight based on the total amount of the treated aqueous solution, the effect will be limited, meaningless, and the balance with other components will be poorly adjusted and uneconomical. Not preferable.

It should be noted that these organic acids may be added not only in one kind, but also in a suitable mixture of two or more kinds, if desired.

Further, the above-mentioned "surfactant" is added mainly for permeating and accommodating a treatment aqueous solution containing a halogen-based compound into the details of the intermediate product 1 of the multilayer ceramic capacitor to realize uniform treatment and to develop gloss. However, any of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants or nonionic surfactants can be used.

Specifically, as the anionic surfactant, a fatty acid salt type, an alkylbenzene sulfonate type, an alkyl sulfate ester type, a linear secondary sulfonate type, a dialkylsulfosuccinic acid ester salt type, a POE alkyl or alkyl phenyl ether is used. Examples thereof include sulfuric acid ester salt type and POE alkyl or alkyl phenyl ether phosphate ester type.

On the other hand, examples of the cationic surfactant include alkylpicolinium chloride type, alkyltriethylammonium chloride type and other quaternary ammonium salt type.

Further, as nonionic surfactants, POE alkylphenyl ether type nonions, POE alkyl ether type nonions, POE polyoxypropylene block polymer type nonions, POE glycol alkyl ester type nonions, sorbitan fatty acid ester type nonions, and sucrose fatty acid ester type nonions. Etc. can be mentioned.

Further, examples of the amphoteric surfactant include alkyl carboxy betaine type, alkyl amino carboxylic acid type, and alkyl imidazoline type.

In addition, examples of the nonionic surfactant include POE alkyl ether, POE alkyl phenyl ether, sucrose fatty acid ester, ethylene glycol and glycerin.

The amount of these surfactants added is appropriately determined depending on the material of the intermediate product 1 of the target laminated ceramic capacitor, the type and concentration of the inorganic acid, and is not particularly limited. In general, the range of 0.0005 to 5.0 wt% is preferable, and the range of 0.001 to 1.5 wt% is more preferable, and the range of 0. The range of 05 to 1.0% by weight is particularly preferable.

If the amount of the surfactant added is less than 0.0005% by weight based on the whole treatment aqueous solution, the amount of the surfactant added is too small to obtain the desired effect, which is not preferable. On the other hand, 5.0% by weight If it exceeds, it is meaningless because the effect is limited, and it is not preferable because the treatment aqueous solution containing the halogen-based compound and the waste liquid thereof are foamed to make the treatment and handling difficult, and it is uneconomical.

In addition, not only one kind of the surfactant but also two or more kinds of plural kinds may be appropriately mixed and added.

The intermediate product 1 of the laminated ceramic capacitor of the present invention is manufactured by the manufacturing method of the intermediate product 1 of the laminated ceramic capacitor of the present invention.

The monolithic ceramic capacitor 10 of the present invention uses the intermediate product 1 of the monolithic ceramic capacitor of the present invention. In this intermediate product 1, the internal electrode 3 and the external electrode 5 are provided at a plurality of positions on both ends or side surfaces thereof, for example, by a known method. Manufactured by electrical connection.

When the intermediate product 1 of the multilayer ceramic capacitor of the present invention is used, and the external electrodes 5 are formed on the both ends or the side surface of the intermediate product 1 so as to be electrically connected to the internal electrodes 3, An ink jet for which the electrode 5 applies/bakes a conductive paste, dips/bakes a conductive paste, prints/bakes a conductive paste, and sprays a conductive ink containing metal powder from a nozzle by a known method. It may be formed by printing/baking by a method, spraying/baking a conductive paste containing a metal powder, or vapor deposition, plating or sputtering of a metal.

That is, the intermediate product 1 of the monolithic ceramic capacitor of the present invention is used, and the external electrode 5 is formed at a plurality of positions on both ends or side surfaces of the intermediate product 1 so as to be electrically connected to the internal electrode 3. .. As the metal material of the external electrode 5, the same materials as those of the internal electrode 3 can be used, and B ₂ O ₃ —SiO ₂ —BaO glass, Li ₂ O—SiO ₂ can be used as the metal material. A glass frit such as a BaO glass may be used.

For example, the case of forming the external electrodes 5 on both ends of the intermediate product 1 of the multilayer ceramic capacitor of the present invention will be described with reference to FIG.

As shown in FIG. 1( d ), when the porous portions 2 a are formed at both ends of the ceramic layer 2 of the intermediate product 1, the internal electrode 3 causes the conductive paste containing the glass frit and the copper powder to pass through. It is applied to both ends of the exposed intermediate product 1 of the monolithic ceramic capacitor and baked in a vacuum firing furnace to form an inner external electrode 5a that is in direct contact with the internal electrode 3. As a result, the external electrode 5a can be directly connected to the internal electrode 3 and the external electrode 5a by intruding the glass frit and the metal powder into the porous portions 2a at both ends of the ceramic layer 2 and firmly integrating them. ..

Next, a first plating layer 5b of nickel or the like is formed on the external electrode 5a, and a second plating layer 5c of solder, tin or the like is further formed on the plating layer 5b, and the laminated ceramics of the present invention is formed. The capacitor 10 is manufactured. By the way, in the present invention, the above-mentioned first and second plated layers 5b and 5c may be omitted depending on the application of the laminated ceramic capacitor 10 of the present invention.

As described above, when the conductive paste containing the glass frit and the copper powder is applied to both ends of the intermediate product 1 of the laminated ceramic capacitor in which the internal electrodes 3 are exposed in a reduced pressure atmosphere, the glass frit and the copper powder are Is desirable because it easily penetrates into the porous portion 2a and easily contacts the internal electrode 3.

In the multilayer ceramic capacitor 10 of the present invention obtained by forming the external electrodes 5 in this manner, the connection and adhesion between the internal electrodes 3 and the external electrodes 5 are extremely good, so that the quality is stable and the excellent dielectric property is obtained. It has characteristics.

As described above, the multilayer ceramic capacitor 10 of the present invention is manufactured by forming the external electrode 5 on the intermediate product 1 of the multilayer ceramic capacitor of the present invention.

Further, in the present invention, as shown in Examples described later, it is carried out by a simple process in which at least an end of the intermediate product 40 of the laminated ceramic capacitor after firing is brought into contact with a treatment aqueous solution containing a halogen compound for a short time. Therefore, the productivity can be remarkably improved. Further, unlike the conventional physical processing using a special dedicated jig, in the present invention, the quality of the product is stable, the defect occurrence rate is low, the yield is improved, and the production cost is increased. The technical problems of the present invention can be solved all at once, for example, a significant reduction can be achieved.

Hereinafter, the present invention will be described in detail based on specific examples.
<Examples 1 to 113>
Test piece BaTiO ₃ was used as the ceramic layer 2, and 300 green sheets in which Ni was used as the internal electrodes 3 were laminated and pressure-bonded to form a laminate, which had a length of 3.15 mm, a width of 1.60 mm, and a thickness of 1.60 mm. A monolithic ceramic capacitor intermediate product 4 was manufactured by cutting into a rectangular parallelepiped having a length of 1.60 mm. The intermediate product 4 was fired to produce an intermediate product 40 of a 300-sheet laminated type multilayer ceramic capacitor as a test piece. The state of the end face of the intermediate product 40 of the multilayer ceramic capacitor thus obtained was measured with a TM3030 tabletop microscope Miniscope manufactured by Hitachi High-Technologies Corporation. The obtained image is shown in FIG. 118 before being processed.

Treatment Aqueous Solution Containing Halogen-Based Compound A treatment aqueous solution containing a halogen-based compound having each composition shown in Tables 1 to 6 was prepared.

<First Embodiment for Manufacturing Intermediate Product 1 of Multilayer Ceramics Capacitor>
The manufacturing process of this embodiment is shown in FIG.
The above test piece was immersed in lime milk (1% calcium hydroxide aqueous solution: for example, Kanto Chemical Co., Ltd. Deer Grade 1), which is a neutralizing agent for neutralizing the halogen compound etching agent, for about 3 minutes. Immerse (step S1). As a result, the above-mentioned neutralizing agent can be internally fed from minute cracks or recesses formed on the entire surface of the intermediate product of the monolithic ceramic capacitor, connecting portions between the external electrodes and the ceramic chip (“surface defects, etc.”). Permeate and/or impregnate.
After washing with water or the like (step S2), the ceramic layer is dissolved by contacting it with a treatment aqueous solution containing sodium fluoride which is each halogen-based compound at room temperature of 25° C.±3° C. under the conditions shown in Tables 1 to 6. At the same time as removing and exposing the internal electrodes to the outside, the lime milk that has penetrated or/and is impregnated into the intermediate product of the laminated ceramic electronic component and the sodium fluoride in the foam treatment liquid undergo a neutralization reaction (step S3) can be done. Further, surface defects and the like can be sealed by changing the neutralizing agent to calcium fluoride by a neutralization reaction.

Further, in a step after the treatment with the treatment aqueous solution, washing with water or the like (step S4), and thereafter, as a measure against adversely affecting the product characteristics by leaving a slight amount of the treatment aqueous solution in the details, lime milk is used again. Immersion treatment in a neutralizer (1% calcium hydroxide aqueous solution) (step S5), washing again with water etc. (step S6), ultrasonic washing for 3 minutes, etching treatment and neutralization of the test piece Processed. As a result, when the remaining etching agent penetrates into the interior from surface defects and the like, it is neutralized by the solidified residue, and the solidified residue seals the surface defects, etc. It is possible to prevent the permeation of the plating solution into the interior of the plating solution, the penetration of the plating solution into the plating process during the formation of the external electrode, and the like.
In the cleaning in steps S2, S4 and S6, ultrasonic cleaning may be used in part or in whole.
The neutralizing agent used in the present invention was neutralized with a 0.1 wt% calcium hydroxide aqueous solution. However, in the present invention, other neutralizing agents such as sodium hydroxide, potassium hydroxide and lithium hydroxide are used. It is possible to use at least one or more selected from alkali metal hydroxides such as and alkaline earth metal hydroxides such as alkali metal carbonates such as sodium carbonate and potassium carbonate.

<Second Embodiment for Manufacturing Intermediate Product 1 of Multilayer Ceramic Capacitor>
Instead of “immersing in a neutralizing agent” in step S5, powdered calcium hydroxide (particle size: 300 nm to 1000 nm) may be used to bring the powdered calcium hydroxide into contact with the laminated ceramic electronic component. After that, ultrasonic cleaning is performed. If necessary, contact with powdered calcium hydroxide and washing are repeated multiple times. As the powder neutralizing agent, similar to the above, in addition to calcium hydroxide, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, etc. At least one selected from the above alkaline earth metal hydroxides can be used.

The state of the end face of the intermediate product of each multilayer ceramic capacitor thus obtained was measured with a TM3030 tabletop microscope Miniscope manufactured by Hitachi High-Technologies Corporation.
The results are shown in Tables 1 to 6 and FIGS. 5 to 118.

<Evaluation>
Regarding the degree of exposure of the internal electrode 3, when the end portion of the internal electrode 3 projects 1 μm or more outward from the end surface of the ceramic layer 2, the end surface or end portion of the internal electrode 3 is flush with the end surface of the ceramic layer 2. In the range of 1 μm to less than 1 μm, the case where the electrode is exposed and exposed to outside is marked with ◯, and the case where the internal electrode 3 is buried in the ceramic layer 2 is marked with x.

-Repetitive reproducibility In the same manner as in each of the examples, a number of 1000 pieces is produced, and 20 pieces are arbitrarily taken out from the intermediate product 40 of each laminated ceramic capacitor and subjected to the same treatment to remove the end surface or the end portion of the internal electrode 3. The exposed state and the porous state of the end portion of the ceramic layer 2 were visually observed from the analysis image and evaluated. In the evaluation of the exposed state of the internal electrode 3 and the state of the porous end portion of the ceramic layer 2, the same can be evaluated as follows: 90% or more: ⊚, less than 90%: 80% or more: The case where it was less than 80% and 60% or more was evaluated as Δ.

It is to be noted that the case where 90% or more of the internal electrode 3 was buried in the ceramic layer 2 before the intermediate product 40 of the laminated ceramic capacitor after the firing was treated was marked with x.

From the results of Tables 1 to 6 and FIGS. 5 to 118, the intermediate product 40 of the multilayer ceramic capacitor shows that the end surface of the internal electrode 3 buried in the ceramic layer 2 by the etching treatment of the treatment aqueous solution containing the halogen-based compound. Alternatively, it was confirmed that the end portion can be exposed or projected outward efficiently in a short time. Further, in spite of the simple treatment with the treatment aqueous solution containing the halogen-based compound, the end surface or the end portion of the internal electrode 3 can be exposed or projected to the outside with a very high probability. It was confirmed that the intermediate product 1 of the multilayer ceramic capacitor of the invention could be obtained.
Further, the Cu paste containing glass frit is applied to the end of the intermediate product 1 of each multilayer ceramic capacitor thus obtained, and baked at a temperature of 800° C. in a reduced pressure atmosphere to form the Cu electrode 5a as a base electrode. After the formation, the Ni-plated electrode 5b and the Sn-plated electrode 5c are sequentially stacked on the outer electrode 5 to attach the external electrode 5, thereby completing the multilayer ceramic capacitor 10 of the present invention.

FIG. 119A is an electron micrograph of an intermediate product of a multilayer ceramic capacitor (ceramic electronic component) in the first embodiment of manufacturing the intermediate product 1 of the multilayer ceramic capacitor, and FIG. 119B is a multilayer ceramic capacitor in the second embodiment. It is an electron microscope photograph of an intermediate product of (ceramics electronic component).
Table 7 below shows the analysis results of the surface components of the ceramic layer in the first embodiment, and Table 8 shows the analysis results of the surface components of the ceramic layer in the second embodiment.
In FIGS. 119A and 119B, the black-colored portion is a solidified residue of the neutralizing agent, and it can be seen that the residue penetrates from the surface defects of the ceramic layer into the inside and seals the surface result. .. From Tables 7 and 8, it is recognized that the ratio of calcium in the case of using the powder is higher than that in the case of using the aqueous solution of calcium hydroxide, and the use of the powder also has a certain sealing effect.

Although the preferred embodiment of the present invention has been described, the present invention is not limited to the above description. For example, although the neutralizing agent is an aqueous solution in the above embodiment, a powdery neutralizing agent having a particle size of about 300 to 1000 nm may be brought into contact with the ceramics. Further, in the manufacturing process shown in FIG. 4, if the etching agent can be sufficiently neutralized by the first immersion of the neutralizing agent (step S1), the steps after step S5 can be omitted. .. In the present invention, when the etching agent may still remain inside the surface defect or the like even in the etching process of step S3 and the cleaning of step S4, or the cleaning water or the plating solution may penetrate inside. In addition, by optionally providing the step S5 and the subsequent steps, the neutralization reaction and the solidification of the residue of the neutralizing agent are effectively prevented from penetrating these, and the internal electrodes and electronic parts inside the ceramic have a longer life. The effect is that it can be kept at.

The present invention is not limited to the manufacture of intermediate products of multilayer ceramic capacitors and multilayer ceramic capacitors, and various types of external electrodes are formed at the ends of the intermediate products of various ceramic electronic components having internal electrodes. The present invention can be applied to the manufacture of electronic components, and more specifically, to the manufacture of, for example, chip inductors, chip LC components, chip arrays, chip filters and the like. Further, the ceramics are not limited to stacking and firing, but can be applied to ceramics molded by any molding method.

1 Intermediate product of multilayer ceramic capacitor (ceramic electronic component) 10 Multilayer ceramic capacitor (ceramic electronic component)
2 Ceramics layer 3 Internal electrode 5 External electrode 110 Conventional multilayer ceramic capacitor (ceramic electronic component)

Claims (12)

After obtaining the ceramics electronic component body in which the periphery of the electronic component including the internal electrodes is coated with ceramics,
A neutralizing agent having a property of neutralizing by reacting with an etching agent is impregnated inside from at least an end portion or a surface defect of the ceramic electronic component body intended to expose the internal electrode,
After that, the etching agent is brought into contact with at least the end portion or end surface of the ceramic electronic component body,
As a result, the ceramics are etched to expose the internal electrodes buried in the ceramics outward from the ceramics, and the neutralizing agent and the etching agent impregnated inside the surface defects and the like are removed. Having neutralized,
A method for manufacturing an intermediate product of a ceramic electronic component, characterized by: After the etching, a neutralizing agent having a property of reacting with the etching agent to be neutralized is impregnated into at least the surface defect of the end portion or the end surface of the ceramic electronic component body intended to expose the internal electrodes. The method for producing an intermediate product of a ceramic electronic component according to claim 1, further comprising a step of: After the etching, a step of contacting a powder of a neutralizing agent having a property of reacting with the etching agent to be neutralized with at least an end portion or an end surface of the ceramic electronic component body intended to expose the internal electrode. The method for producing an intermediate product of a ceramic electronic component according to claim 1, further comprising: The method for producing an intermediate product of a ceramic electronic component according to claim 1, wherein the residue of the neutralizing agent after being neutralized is solidified inside the surface defect or the like. At least an end portion or an end surface of the ceramic electronic component body is immersed in a treatment aqueous solution containing an etching agent or a neutralizing solution containing the neutralizing agent, or at least an end portion or an end surface of the ceramic electronic component body. By coating, spraying or spraying the treatment aqueous solution or the neutralizing solution on the above, the treatment aqueous solution is brought into contact with or impregnated with the neutralizing solution to at least an end portion or an end face of the ceramic electronic component body. The method for producing an intermediate product of the ceramic electronic component according to any one of claims 1 to 4. The neutralizing agent is impregnated or brought into contact with the entire body of the ceramic electronic component, and the neutralizing agent impregnated or brought into contact with the entire body of the ceramic electronic component is neutralized by the etching agent. ceramic electronic component manufacturing method of the intermediate product of according to any one of claims 1 to 5, wherein. By adjusting at least one of the concentration, temperature or pressure of the neutralizing agent or the contact time between the neutralizing agent and the ceramic electronic component body, the neutralization is performed inside the surface defects and the like. The method for producing an intermediate product of a ceramic electronic component according to any one of claims 1 to 6, wherein the agent is impregnated with the agent. The etching agent is a halogen-based compound and is sodium fluoride, sodium acid fluoride, potassium fluoride, potassium acid fluoride, ammonium acid fluoride, neutral ammonium fluoride, sodium chloride, potassium chloride, ammonium chloride, sodium bromide. And at least one selected from potassium bromide and ammonium bromide. 8. The method for producing an intermediate product of a ceramic electronic component according to claim 1, wherein the intermediate product is a ceramic electronic component. The method for producing an intermediate product of a ceramic electronic component according to claim 8, wherein the treatment aqueous solution containing the halogen-based compound has a concentration of 0.001 to 10.0% by weight. The neutralizing agent is selected from alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkaline earth metal hydroxides such as calcium hydroxide. The method for producing an intermediate product of ceramic electronic components according to claim 8 or 9, wherein at least one selected from the above. From a ceramic electronic component body in which the periphery of an electronic component including internal electrodes is coated with ceramics, in an intermediate product of ceramic electronic components in which the internal electrodes are exposed by an etching agent,
A neutralizing agent having a property of reacting with an etching agent impregnated in the inside from a surface defect or the like of an end portion or an end surface of the ceramic electronic component element body and the etching agent are reacted and solidified. An intermediate product of a ceramic electronic component, characterized in that the residue of the neutralizing agent is filled inside the surface defects and the like . A ceramic electronic component body whose periphery is coated with ceramics,
Internal electrodes exposed by an etching agent from this ceramic electronic component body,
External electrodes electrically connected to the internal electrodes at a plurality of positions on both ends or side surfaces of the ceramic electronic component element body,
Generated by neutralization of the etching agent and a neutralizing agent that is filled inside the surface of the ceramic electronic component body exposing the internal electrodes and has the property of neutralizing by reacting with the etching agent. And the solidified residue of the neutralizing agent,
A ceramic electronic component having: