WO2016114091A1 - Procédé de production d'un produit intermédiaire de condensateur céramique multicouche, solution de traitement aqueuse contenant un composé d'halogène utilisé pour la production d'un produit intermédiaire de condensateur céramique multicouche, produit intermédiaire de condensateur céramique multicouche, procédé de fabrication d'un condensateur céramique multicouche et condensateur céramique multicouche - Google Patents

Procédé de production d'un produit intermédiaire de condensateur céramique multicouche, solution de traitement aqueuse contenant un composé d'halogène utilisé pour la production d'un produit intermédiaire de condensateur céramique multicouche, produit intermédiaire de condensateur céramique multicouche, procédé de fabrication d'un condensateur céramique multicouche et condensateur céramique multicouche Download PDF

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WO2016114091A1
WO2016114091A1 PCT/JP2015/086191 JP2015086191W WO2016114091A1 WO 2016114091 A1 WO2016114091 A1 WO 2016114091A1 JP 2015086191 W JP2015086191 W JP 2015086191W WO 2016114091 A1 WO2016114091 A1 WO 2016114091A1
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ceramic capacitor
multilayer ceramic
acid
intermediate product
aqueous solution
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PCT/JP2015/086191
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English (en)
Japanese (ja)
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森家英幸
森家圭一郎
森家洋晃
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株式会社北陸濾化
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Priority to CN201580076944.XA priority Critical patent/CN107251177B/zh
Publication of WO2016114091A1 publication Critical patent/WO2016114091A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors

Definitions

  • the present invention relates to a method for producing an intermediate product of a multilayer ceramic capacitor, a treatment aqueous solution containing a halogen compound used in the production of an intermediate product of the multilayer ceramic capacitor, an intermediate product of the multilayer ceramic capacitor, a method for producing the multilayer ceramic capacitor, and a multilayer ceramic capacitor. It is about.
  • a multilayer ceramic capacitor is formed by alternately laminating a plurality of ceramic layers and internal electrodes, and crimping and cutting the multilayer body to obtain a green chip, that is, a multilayer ceramic capacitor element, and then the multilayer ceramic capacitor element.
  • the body is fired, and then external electrodes are formed on both end faces of the fired multilayer ceramic capacitor body (see, for example, Patent Document 1 and Patent Document 2).
  • the multilayer ceramic capacitor element body and the multilayer ceramic capacitor element body obtained by firing the element body are referred to as an intermediate product of the multilayer ceramic capacitor and an intermediate product of the fired multilayer ceramic capacitor, respectively.
  • Such a multilayer ceramic capacitor is manufactured through the following steps. First, as shown in FIG. 118 (a), a plurality of ceramic layers 2 and internal electrodes 3 are alternately laminated, and the laminated body is crimped and cut to obtain an intermediate product 4 of the laminated ceramic capacitor. In the intermediate product 4 of the multilayer ceramic capacitor before firing, as shown in FIG. 118 (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. 118B, the internal electrode 3 is buried in the ceramic layer 2 due to the difference in thermal expansion coefficient and thermal contraction rate between the ceramic layer 2 and the internal electrode layer 3.
  • the end portion of the fired multilayer ceramic capacitor intermediate product 40 is physically polished and removed, and the end surface of the internal electrode 3 is exposed to the outside from the end surface of the ceramic layer 2, and the multilayer ceramic capacitor intermediate product 100.
  • the external electrodes 5 and 5 are respectively provided at both ends of the intermediate product 100 (see FIG. 118 (d)).
  • the multilayer ceramic capacitor 110 is manufactured through this process.
  • the end of the ceramic body (intermediate product 40 of the fired multilayer ceramic capacitor 40) is physically polished and removed to expose the end face of the internal electrode 3 outward from the end face of the ceramic layer 2. It is disclosed that an aqueous solution in which a complexing agent is dissolved, a ceramic body and an abrasive are put in a polishing tank to polish the ceramic body (see Patent Document 1).
  • Patent Document 1 a complexing agent causes a solubilizing action in which abrasive powder and polishing debris that are difficult to dissolve in water are diffused into water, resulting in a state change in water. It has been disclosed that such a change in the state of water prevents the diffused polishing powder and polishing scraps from penetrating water into the gap between the ceramic layer and the internal electrode.
  • the complexing agent may be a gluconate whose composition formula is represented by C6H11O7M and M is selected from Na, K, Mg, and Ca.
  • a complexing agent a citrate having a composition formula of C6H8O7 can be used (see Patent Document 1).
  • a carboxylic acid-based complexing agent can be used to cause a change of state in water, and in particular, gluconates and citrates as described above can be used (patents). Reference 1).
  • the end portion of the ceramic layer 2 in the intermediate product 40 of the fired multilayer ceramic capacitor is physically polished and removed, and the end face of the internal electrode 3 is exposed. Since the external electrode 5 is provided from the outside, there is a need to select a polishing tip according to the size of the intermediate product 40, and the work is complicated, troublesome, and special equipment is required. Has occurred.
  • the multilayer ceramic capacitor is small and is composed of a laminate of an extremely large number of ceramic layers 2 and internal electrodes 3, problems such as defective products are likely to occur, yield and quality deteriorate.
  • the end surface of the intermediate product 40 of the multilayer ceramic capacitor is physically polished by a dedicated jig such as shot blasting or barrel polishing, the polished surface is scraped or roughened, or the end portion of the ceramic layer 40 is polished.
  • the damaged portion 3a is formed at the end of the internal electrode 3, or the shavings 2b adhere to the end surface of the intermediate product 40, thereby causing poor contact between the internal electrode 3 and the external electrode 5.
  • the external electrode 5 cannot be provided in a state of being firmly and securely adhered to the internal electrode 3.
  • the abrasive used here is extremely small, so that it is very difficult to separate the intermediate product 40 from the abrasive after the polishing. As a result, problems such as deterioration in quality, variation in quality, and deterioration in workability occur.
  • the dedicated jig is consumed, and if it is not polished while frequently checking its consumption state, the processing accuracy is lowered and is not good. Problems such as generation of non-defective products also arise.
  • the multilayer structure of the intermediate product 40 is destroyed by the impact, or the electrode is damaged. Will also occur.
  • Patent Document 1 discloses or suggests that the complexing agent causes polishing powder or polishing debris diffused into water to enter the gap between the ceramic layer and the internal electrode and prevent water from entering the gap. In this way, it is disclosed that it is possible to prevent the ceramic body from cracking by suppressing the intrusion of water into the ceramic body and preventing the expansion of water due to heat during the formation of the external electrode. ing.
  • Patent Document 1 it is possible to prevent cracks in the ceramic body (intermediate product 40 of the laminated ceramic capacitor after firing), but the above-mentioned disadvantages caused by physically polishing the ceramic body are solved. It is judged that it cannot be done.
  • a mixture comprising 25% by weight of citric acid and 75% by weight of sodium citrate was prepared as a complexing agent. 10 parts by weight of this complexing agent was dissolved in 100 parts by weight of water to obtain an aqueous complexing agent solution of about 9.1% by weight.
  • the ceramic body after firing and before polishing (intermediate product 40 of the fired multilayer ceramic capacitor) is immersed in warm water of 40 ° C. ⁇ 2 ° C. for 3 minutes, washed, and then the complexing agent aqueous solution of 40 ° C. ⁇ 2 ° C. In this case, after being immersed for 5 hours, it was washed with water and ultrasonically washed for 3 minutes. When the treated ceramic body was observed with the naked eye, there was no change and no etching was observed.
  • the present invention has been made to solve the above-described problems, and can significantly improve the productivity, and the adhesion between the internal electrode and the external electrode is extremely good, the reliability is high, and the yield is high.
  • the manufacturing method of the intermediate product of the multilayer ceramic capacitor, the treatment aqueous solution containing the halogen-based compound used for the manufacture of the intermediate product of the multilayer ceramic capacitor, and the multilayer ceramic which are extremely good in quality, and have high quality such as electrical characteristics and are stable
  • An object of the present invention is to provide an intermediate product of a capacitor, a method for manufacturing a multilayer ceramic capacitor, and a multilayer ceramic capacitor.
  • a method for manufacturing an intermediate product of a multilayer ceramic capacitor according to the present invention includes alternately stacking a plurality of ceramic layers and internal electrodes, and crimping and cutting the multilayer body to obtain an intermediate layer of the multilayer ceramic capacitor. After the product is obtained, the intermediate product is fired, and then the treated aqueous solution containing the halogen-based compound is brought into contact with at least the end portion of the fired laminated ceramic capacitor intermediate product, thereby the end of the ceramic layer. The portion is etched to expose the end face or the end portion of the internal electrode buried in the ceramic layer to the outside from the end face of the ceramic layer.
  • the present invention has the greatest feature in that an etching method using a treatment aqueous solution containing a halogen compound is employed.
  • contact means that the treatment aqueous solution containing the halogen-based compound of the present invention, which will be described later, touches the end portion or the whole of the intermediate product of the multilayer ceramic capacitor after firing.
  • the treatment aqueous solution containing the halogen-based compound of the present invention is not particularly limited as long as it can touch at least the end portion of the intermediate product of the fired multilayer ceramic capacitor. Specifically, for example, the end portion or the whole of the intermediate product is immersed in the treatment aqueous solution, or the treatment aqueous solution is applied, sprayed or sprayed on the end portion or the whole of the intermediate product.
  • etching refers to erosion of the bonding portion between the ceramic particles at the end of the intermediate product of the multilayer ceramic capacitor after firing, or permeation between the ceramic particles at the end of the intermediate product. It means that the particles are peeled or separated, and further, the ceramic particles are dispersed in a treatment aqueous solution containing a halogen compound. In this case, it is desirable to perform ultrasonic treatment in order to more effectively separate and release the ceramic particles and further disperse the ceramic particles in the treatment aqueous solution.
  • the end face or the end part of the internal electrode embedded in the ceramic layer in the intermediate product of the fired multilayer ceramic capacitor can be exposed outward from the end face of the ceramic layer.
  • the internal electrode is printed and baked with a conductive paste containing a metal powder, and the printing by an ink jet method in which the conductive ink containing the metal powder is sprayed from a nozzle.
  • a conductive paste containing a metal powder is printed and baked with a conductive paste containing a metal powder
  • the printing by an ink jet method in which the conductive ink containing the metal powder is sprayed from a nozzle.
  • At least an end portion of the intermediate product of the multilayer ceramic capacitor is immersed in a treatment aqueous solution containing a halogen compound, or the treatment is applied to at least the end portion of the intermediate product. It is desirable that the treatment aqueous solution is brought into contact with at least an end portion of the intermediate product by applying or spraying or spraying the aqueous solution.
  • the contact time between at least the end of the intermediate product of the multilayer ceramic capacitor and the treatment aqueous solution containing the halogen compound, the temperature of the treatment aqueous solution, or the treatment aqueous solution By adjusting one or more of the halogen compound concentrations, the oxide film generated during firing is removed from the end surface of the internal electrode, and the end surface is activated. What removed the edge part of the ceramic layer which covers a part is desirable.
  • the contact time between at least the end of the intermediate product of the multilayer ceramic capacitor and the treatment aqueous solution containing the halogen compound, the temperature of the treatment aqueous solution, or the treatment aqueous solution By adjusting any one or more of the halogen compound concentrations, the end face or the end of the internal electrode is exposed or protrudes outward within the range of 1 to 2.5 ⁇ m from the end face of the ceramic layer. Is desirable.
  • the contact time between at least the end of the intermediate product of the multilayer ceramic capacitor and the treatment aqueous solution containing the halogen compound, the temperature of the treatment aqueous solution, or the treatment aqueous solution By adjusting one or more of the halogen compound concentrations, a porous part consisting of pores and porous parts is formed at the end of the ceramic layer within a depth of 3 ⁇ m from the end face of the ceramic layer. What is done is desirable.
  • a treatment aqueous solution containing a halogen compound according to the present invention used to solve the above-mentioned problems, wherein the halogen compound contained in the treatment aqueous solution is a fluorine compound, a chlorine compound or a bromine compound. What is at least one selected is desirable.
  • the halogen compound is sodium fluoride, sodium acid fluoride, potassium fluoride, potassium acid fluoride, ammonium acid fluoride, neutral ammonium fluoride, sodium chloride, What is at least 1 sort (s) chosen from potassium chloride, ammonium chloride, sodium bromide, potassium bromide, or ammonium bromide is desirable.
  • the treatment aqueous solution containing the halogen compound of the present invention is added with an etching accelerator for promoting etching.
  • the etching accelerator is at least one selected from hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, hypochlorous acid, phosphoric acid, boric acid, polyphosphoric acid or polyboric acid. More than one inorganic acid or alkali metal salt or ammonium salt thereof is desirable.
  • an intermediate product of the multilayer ceramic capacitor is added with a surface stabilizer that stabilizes the activated surface of the intermediate product after etching.
  • the surface stabilizer is preferably a protective film forming material comprising at least one organic acid selected from oxycarboxylic acid or dicarboxylic acid, or an alkali metal salt or ammonium salt thereof.
  • 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
  • Examples of the intermediate product of the multilayer ceramic capacitor of the present invention include those manufactured by the method for manufacturing the intermediate product of the multilayer ceramic capacitor of the present invention.
  • the manufacturing method of the multilayer ceramic capacitor of the present invention for solving the above-described problems is such that the intermediate product of the multilayer ceramic capacitor of the present invention is electrically connected to internal electrodes at both ends or a plurality of locations on the side surface. It is desirable that an external electrode is formed.
  • the external electrode is coated and baked with a conductive paste, dipped and baked with a conductive paste, printed and baked with a conductive paste, and conductive ink containing a metal powder is atomized.
  • the multilayer ceramic capacitor of the present invention is manufactured by the method for manufacturing a multilayer ceramic capacitor of the present invention.
  • the productivity of the intermediate product of the multilayer ceramic capacitor and the multilayer ceramic capacitor is 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, and the quality such as electrical characteristics is high and stable.
  • Intermediate products and multilayer ceramic capacitors can be obtained.
  • FIG. 1 (a) is a schematic cross-sectional view of an intermediate product of a multilayer ceramic capacitor before firing and a partial enlarged cross-sectional view thereof, and (b) is a schematic cross-sectional view of an intermediate product of a multilayer ceramic capacitor after firing and a partial enlarged view thereof.
  • Sectional view (c) is a schematic 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 an enlarged sectional view of a part thereof.
  • FIG. 2 is a schematic cross-sectional view of a multilayer ceramic capacitor of the present invention obtained by attaching an external electrode to an intermediate product of the multilayer ceramic capacitor of the present invention, and a partially enlarged sectional view thereof.
  • 3 is a partially broken schematic cross-sectional view showing a multilayer ceramic capacitor according to the present invention. It is a schematic diagram which shows the manufacturing process of the intermediate product of a multilayer ceramic capacitor.
  • 4 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 1.
  • 3 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 2.
  • 4 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 3.
  • 4 is an electron micrograph of an intermediate body of a multilayer ceramic capacitor according to Example 4.
  • 4 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 5.
  • 6 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 6.
  • 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 7.
  • 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 8.
  • 7 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 9.
  • 10 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 10.
  • 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 11.
  • 14 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 12.
  • 14 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 13.
  • 18 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 14.
  • 18 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 15.
  • 18 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 16.
  • 18 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 17.
  • FIG. 18 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 18.
  • 18 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 19.
  • 18 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 20.
  • 14 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 21.
  • FIG. 14 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 22.
  • 14 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 23.
  • FIG. 14 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 24.
  • FIG. FIG. 26 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 25.
  • FIG. 14 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 26.
  • FIG. 18 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 27.
  • FIG. 42 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 28.
  • FIG. FIG. 26 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 29.
  • FIG. 4 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 30.
  • FIG. 2 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 31.
  • FIG. FIG. 14 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 32.
  • FIG. 14 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 33.
  • FIG. 14 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 34.
  • FIG. 26 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 35.
  • FIG. 14 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 36.
  • FIG. 42 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 37.
  • FIG. 14 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 38.
  • FIG. 42 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 39.
  • FIG. 42 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 40.
  • 2 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 41.
  • FIG. FIG. 14 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 42.
  • FIG. 4 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 43.
  • FIG. 14 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 44.
  • 14 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 45.
  • FIG. 14 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 46.
  • FIG. 14 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 47.
  • 42 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 48.
  • 14 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 49.
  • FIG. 14 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 50.
  • FIG. 2 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 51.
  • FIG. 6 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 52.
  • FIG. FIG. 14 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 53.
  • FIG. 16 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 54.
  • FIG. 18 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 55.
  • FIG. 18 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 56.
  • 18 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 57.
  • FIG. 19 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 58.
  • FIG. 20 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 59.
  • FIG. 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 60.
  • FIG. 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 61.
  • FIG. 18 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 62.
  • FIG. 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 63.
  • FIG. 18 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 64.
  • 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 65.
  • 18 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 66.
  • FIG. 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 67.
  • FIG. 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 68.
  • 14 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 69.
  • 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 70.
  • FIG. 7 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 71.
  • 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 72.
  • FIG. 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 73.
  • FIG. 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 74.
  • FIG. 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 75.
  • FIG. 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 76.
  • 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 77.
  • 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 78.
  • 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 79.
  • 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 80.
  • FIG. 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 81.
  • 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 82.
  • FIG. 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 83.
  • FIG. 18 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 84.
  • 10 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 85.
  • FIG. 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 86.
  • FIG. 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 87.
  • FIG. FIG. 10 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 88.
  • FIG. 10 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 89.
  • FIG. 7 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 90.
  • FIG. 2 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 91.
  • FIG. 10 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 92.
  • FIG. 10 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 93.
  • FIG. 10 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 94.
  • 90 is an electron micrograph of an intermediate of the multilayer ceramic capacitor according to Example 95.
  • FIG. 10 is an electron micrograph of an intermediate of a multilayer ceramic capacitor according to Example 96.
  • FIG. FIG. 5 is an electron micrograph of the intermediate of the multilayer ceramic capacitor according to Example 97.
  • FIG. 9 is an electron micrograph of the intermediate of the multilayer ceramic capacitor according to Example 98.
  • FIG. 5 is an electron micrograph of the intermediate of the multilayer ceramic capacitor according to Example 99.
  • FIG. 3 is an electron microscope photograph of an intermediate of the multilayer ceramic capacitor according to Example 100.
  • 2 is an electron microscope photograph of an intermediate of a multilayer ceramic capacitor according to Example 101.
  • FIG. 3 is an electron microscope photograph of an intermediate of the multilayer ceramic capacitor according to Example 102.
  • 4 is an electron microscope photograph of an intermediate of the multilayer ceramic capacitor according to Example 103.
  • 6 is an electron microscope photograph of an intermediate of the multilayer ceramic capacitor according to Example 104.
  • 4 is an electron microscope photograph of an intermediate of the multilayer ceramic capacitor according to Example 105.
  • 4 is an electron microscope photograph of an intermediate of a multilayer ceramic capacitor according to Example 106.
  • 6 is an electron microscope photograph of an intermediate of the multilayer ceramic capacitor according to Example 107.
  • FIG. 2 is an intermediate product of a multilayer ceramic capacitor after firing, and is an electron micrograph before the intermediate product is treated with a halogenated compound aqueous solution according to the present invention.
  • FIG. 2 is a schematic cross-sectional view and a partially enlarged cross-sectional view of the multilayer ceramic capacitor of the present invention obtained by attaching an external electrode to the intermediate product of the obtained multilayer ceramic capacitor of the present invention.
  • FIG. 1 shows an intermediate product 1 of a multilayer ceramic capacitor according to the present invention and a manufacturing process schematic diagram of the multilayer ceramic capacitor 10 of the present invention obtained using the intermediate product 1, and FIG. 2 shows the multilayer ceramic capacitor of the present invention.
  • 10 shows a partial sectional schematic cross-sectional view.
  • the intermediate product 1 of the multilayer ceramic capacitor according to the present invention shown in FIG. 1 and the multilayer ceramic capacitor 10 according to the present invention are manufactured by the following method.
  • a plurality of ceramic layers 2 and internal electrodes 3 are alternately laminated, and the laminated body is crimped and then cut into a predetermined size to obtain an intermediate product 4 of the laminated ceramic capacitor.
  • the laminated body is crimped and then cut into a predetermined size to obtain an intermediate product 4 of the laminated ceramic capacitor.
  • the end surfaces of the internal electrodes 3 are alternately exposed to the outside through the ceramic layer 2 on both end surfaces of the intermediate product 4.
  • the internal electrode 3 is laminated and formed so as to achieve the above state.
  • the fired multilayer ceramic capacitor intermediate product 40 has the internal electrode 3 as shown in FIG. Due to the difference in thermal contraction rate between the ceramic layer 2 and the internal electrode 3, the end surface or the end of the ceramic layer 2 is buried in the ceramic layer 2, and the contact between the internal electrode 3 and the external electrode 5 described later deteriorates. .
  • the end portion of the intermediate product 40 is etched by being brought into contact with a treatment aqueous solution containing the halogen-based compound of the present invention, which will be described later, thereby, as shown in FIG.
  • the intermediate product 1 of the multilayer ceramic capacitor of the present invention is manufactured by exposing or projecting the end face or end portion of the internal electrode 3 in the intermediate product 40 outward from the end surface of the ceramic layer 2.
  • the treated aqueous solution is etched into the end of the intermediate product 40.
  • the ceramic particles erode the joints between the ceramic particles, or the ceramic particles are separated or separated from each other at the end of the intermediate product 40, or the separated or separated ceramic particles are dispersed in the treatment aqueous solution.
  • the end face or end portion of the internal electrode 3 embedded in the ceramic layer 2 is exposed or protruded outward from the end face of the ceramic layer 2 to produce the intermediate product 1 of the multilayer ceramic capacitor of the present invention.
  • the multilayer ceramic capacitor 10 of the present invention has external electrodes 5 formed at both ends of the intermediate product 1 of the multilayer ceramic capacitor of the present invention by, for example, a known method. It is manufactured by forming.
  • the intermediate product 1 of the multilayer ceramic capacitor of the present invention is manufactured, and then an external electrode is provided on the obtained intermediate product 1 by, for example, a known method. Since the multilayer ceramic capacitor 10 is manufactured, in order to avoid duplication, in the following, the intermediate product 1 of the multilayer ceramic capacitor of the present invention will be mainly described in detail, and then the multilayer 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 dielectric properties. Specifically, it is a ferroelectric material having a high relative permittivity but a large loss. Alternatively, the dielectric constant may be as low as about 100 or less, but the dielectric constant may be low.
  • the intermediate product 1 of the multilayer ceramic capacitor of the present invention includes a ceramic layer 2 in which a ferroelectric material such as barium titanate is used, or a material in which this ferroelectric material is used as a main component.
  • a ferroelectric material such as barium titanate
  • a material in which this ferroelectric material is used as a main component as the other ceramic layer 2, one using a paraelectric material such as forsterite, aluminum oxide, barium magnesium niobate, or barium neodynate, or one using this paraelectric material as a main component, etc. Is mentioned.
  • FIG. 3 shows the method for manufacturing the intermediate product 4 of the multilayer ceramic capacitor in more detail. That is, the multilayer ceramic capacitor intermediate product 4 is manufactured by a method similar to the conventional method. Specifically, for example, a dielectric ceramic powder such as barium titanate and a binder solution are sufficiently mixed and dispersed. After the slurry is formed and the slurry is formed into a sheet to obtain the dielectric sheet 12, the conductive sheet 13 to be the internal electrode 3 is printed on the dielectric sheet 12 to obtain the green sheet 11. A plurality of the green sheets 11 are laminated and pressure-bonded, and the obtained laminate 110 is cut into a predetermined size. The intermediate product 4 of the multilayer ceramic capacitor thus obtained is fired in a firing furnace 20, and the fired multilayer ceramic capacitor intermediate product 40 is manufactured.
  • a dielectric ceramic powder such as barium titanate and a binder solution are sufficiently mixed and dispersed.
  • the conductive sheet 13 to be the internal electrode 3 is printed on the dielectric sheet 12 to obtain the green sheet 11.
  • the thickness of each layer and the number of stacked layers are not particularly limited.
  • the ceramic layer 2 preferably has a thickness in the range of 0.5 to 50 ⁇ m
  • the internal electrode 3 has a thickness in the range of 0.01 to 3.5 ⁇ m.
  • the number is preferably 2 ⁇ m or less
  • the number of stacked layers is not particularly limited, but examples include those having 10 or more layers and exceeding 1000 layers.
  • the method for forming the internal electrode is not particularly limited.
  • the internal electrode is printed and baked with a conductive paste containing a metal powder, or a conductive ink containing a metal powder.
  • a conductive paste containing a metal powder or a conductive ink containing a metal powder.
  • Examples include those formed by printing / baking by an ink jet method in which a mist is sprayed from a nozzle, spraying / baking of a conductive paste containing a metal powder, or metal deposition, plating, or sputtering.
  • the metal powder used for the conductive paste or conductive ink used as the internal electrode 3 is composed of a single metal such as Ag, Pd, Pt, Au, Pb, Sn, Cd, Ti, Zn, Ni, Co or Cu. Examples thereof include metal powders, and metal powders made of an alloy containing at least one selected from simple metals. These metal powders may use only 1 type, or may use 2 or more types. These metal materials can be used for vapor deposition, plating, or sputtering.
  • the metal material of the internal electrode 3 is preferably one that is not oxidized in the firing of the intermediate product 40 of the multilayer ceramic capacitor.
  • a noble metal such as Pt, Pd, Au, or an Ag—Pd alloy is used. Since it is expensive, it is desirable to use a base metal such as Ni, Co or Cu. Such a base metal is oxidized in a high-temperature oxidizing atmosphere, so it must be performed in a reducing atmosphere under a low oxygen partial pressure. In this case, since the ceramic layer 2 may be reduced to become a semiconductor, it is desirable to use the ceramic layer 2 that does not become a semiconductor even when fired in a reducing atmosphere under a low oxygen partial pressure. It is desirable to use dielectric ceramics described in Japanese Patent Publication Nos. 61-14611 and 7-272971.
  • the intermediate product 40 of the laminated ceramic capacitor after firing has an end face or end portion of the internal electrode 3 due to a difference in thermal contraction rate between the ceramic layer 2 and the internal electrode 3.
  • the ceramic layer 2 is buried in the ceramic layer 2, and contact with the external electrode 5 described later may be deteriorated.
  • the end surface or end portion of the internal electrode 3 embedded in the ceramic layer 2 is exposed or protrudes outward from the end surface of the ceramic layer 2.
  • a treatment aqueous solution containing the halogen compound of the present invention is applied or sprayed or sprayed on at least the end of the intermediate product 40, or the end or whole of the intermediate product 40 is treated with the halogen compound. What is necessary is just to immerse in the aqueous solution, and in this way, the treatment aqueous solution containing the halogen-based compound may be brought into contact with at least the end portion of the intermediate product 40 of the multilayer ceramic capacitor.
  • either 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 compound, the temperature of the treatment aqueous solution, or the concentration of the halogen compound in the treatment aqueous solution is adjusted one or more of these, the oxide film generated during firing is removed on the surface of the end portion of the internal electrode 3 by etching to activate the surface, and the ceramic covering the end portion of the internal electrode 3 It is desirable to remove the edge of layer 2.
  • the contact time when contacting at least the end of the multilayer ceramic capacitor intermediate product 40 with the treatment aqueous solution containing the halogen-based compound, the contact time includes the temperature of the treatment aqueous solution and the concentration of the halogen-based compound.
  • the range is 30 seconds to 100 minutes, preferably 1 to 75 minutes, particularly preferably 3 to 60 minutes, and the processing temperature is generally room temperature to 60 ° C.
  • the concentration of the halogen-based compound is preferably in the range of 0.001 to 10.0% by weight, preferably Is in the range of 0.01 to 5.0% by weight, particularly preferably in the range of 0.05 to 3.5% by weight.
  • the treatment aqueous solution may be applied to at least the end of the intermediate product 40 within a range of 30 seconds to 100 minutes as necessary. Just spray it.
  • the intermediate product 1 of the multilayer ceramic capacitor of the present invention is manufactured as shown in FIG. In this way, the technical problem of the present invention can be solved.
  • the end face or end of the internal electrode 3 is flush with the end face of the ceramic layer 2 when contacting at least the end of the intermediate product 40 of the multilayer ceramic capacitor with the treatment aqueous solution containing the halogen compound. It is desirable to expose or protrude outward in the range of 2.5 ⁇ m. 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 the same as described above. It is desirable to adjust any one or more of the compound concentrations.
  • the end of the internal electrode 3 is moved from the end surface of the ceramic layer 2 to 0.05 to 0.5 by increasing the contact time with the above-described conditions, that is, the treatment aqueous solution, or controlling the concentration and temperature of the treatment aqueous solution. It is more desirable to make it in the range of 2 ⁇ m, and it is even more desirable to project outward in the range of 0.1 to 1.5 ⁇ m.
  • the external electrode 5 is formed at both ends of the intermediate product 1.
  • the external electrode 5 is not only in contact with the end face of the internal electrode 3, but the external electrode 5 is in contact with the entire protruding end of the internal electrode 3, the internal electrode 3 and the external electrode 5 Since the contact area is increased, the adhesion between the external electrode 5 and the internal electrode 3 is strengthened, and the contact between the electrodes 3 and 4 is further improved. It improves.
  • the contact time between at least the end of the fired multilayer ceramic capacitor intermediate product 40 and the treatment aqueous solution containing the halogen compound, the temperature of the treatment aqueous solution, or the halogen compound in the treatment aqueous solution is 3 ⁇ m 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.
  • the metal of the external electrode 5 is formed when the external electrode 5 is formed at the end.
  • the component enters the porous portion 2a and is connected to the internal electrode 3 in a state where the external electrode 5 is firmly adhered.
  • the treatment aqueous solution containing the halogen-based compound of the present invention is used for the treatment of at least both ends of the intermediate ceramic capacitor intermediate product 1 of the present invention.
  • the halogen-based compound in this treatment aqueous solution include fluorine-based compounds and chlorine. At least one or more compounds selected from the group compounds or bromine compounds are listed as active ingredients. Specific examples of these halogen compounds include those mentioned above, and among these, A fluorine-based compound is most desirable for efficiently solving the problems of the present invention.
  • the fluorine compound is at least one 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 protrudes the end face or end portion of the internal electrode 3 from the end face of the intermediate product 40 of the multilayer ceramic capacitor, or effectively forms an oxide film on the surface of the intermediate product 40. From these viewpoints, it is desirable that the treatment aqueous solution is added with an etching accelerator for promoting etching in addition to the halogen-based compound. .
  • the etching accelerator examples include 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.
  • 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.
  • ammonium salts may be mentioned.
  • the same or different kinds of inorganic acids and salts thereof may be used in combination.
  • these salts include alkali metal salts such as sodium and potassium. If desired, alkaline earth metal salts such as magnesium and calcium may be used.
  • the concentration of the inorganic acid or a 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. A range is desirable. 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 exceeds 10.0% by weight, the ceramic layer 2 is excessively etched or the internal electrode 3 is dissolved. Since it may occur, it is not preferable. In this case, when a plurality of kinds of inorganic acids or salts thereof are used, it is desirable that the concentration of the total amount be within the above range.
  • two or more kinds of inorganic acids may be mixed and used in the treatment aqueous solution containing the halogen compound.
  • 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 acidic ammonium 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 its transportation and storage are various. This is desirable because it can be handled easily as a result of no legal restrictions.
  • the end portion of the ceramic layer 2 in the intermediate product 40 in contact with the treatment aqueous solution is The end face or end of the internal electrode 3 embedded in the ceramic layer 2 after being etched and removed is exposed or protrudes outward, and the oxide film and the inert film on the treated surface of the intermediate product 40 are removed. Activated.
  • the treatment 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.
  • a surface stabilizer for protecting and stabilizing 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.
  • the protective film stabilizes the active surface and delays the formation of an oxide film by air.
  • 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 bind to each other.
  • a protective film is formed on the active surface of the intermediate product 40, and the oxidation of the active surface is suppressed by this protective film.
  • the surface stabilizer examples include at least one organic acid selected from oxycarboxylic acid or dicarboxylic acid, or a protective film-forming substance made of an alkali metal salt or ammonium salt thereof.
  • the substance examples include those described above, and among these, it is particularly preferable to use a substance having a cyclic structure such as a phenyl group. Specifically, for example, gallic acid, pyrogallol or tannin, or an alkali metal thereof. Most preferred is a salt or ammonium salt.
  • the concentration of the surface stabilizer is generally in the range of 0.001 to 10% by weight in the aqueous treatment solution, preferably 0.05 for the purpose of improving the quality by forming a stable protective film. It is desirable that the content be in the range of ⁇ 5% by weight, particularly preferably in the range of 0.1 ⁇ 3.5% by weight.
  • the treatment aqueous solution containing a hamgen compound may be a treatment aqueous solution containing a one-component hamgen compound in which a hamgen compound and a surface stabilizer coexist, or contains a hamgen compound.
  • a two-part type of a treatment aqueous solution and a treatment aqueous solution containing a surface stabilizer is prepared.
  • 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.
  • 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.
  • a treatment aqueous solution containing a hamgen-based compound is put into a treatment tank, and the intermediate product 40 of the multilayer ceramic capacitor is immersed in the treatment tank to form an active surface.
  • a protective agent may be added to form a protective film on the active surface.
  • an aqueous solution containing no inorganic acid may be used in the aqueous treatment solution containing the surface stabilizer.
  • the concentration of the inorganic acid may be prepared in the same manner as described above.
  • a stronger protective film is formed on the end face or end portion of the exposed or protruding internal electrode 3 in the intermediate product 40 of the multilayer ceramic capacitor as compared with the ceramic layer.
  • the reason is that a uniform electric double layer is formed between the metal ions generated from the end face or 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 a more dense protective film is formed on the exposed surface of the internal electrode 3 due to bonding of the carboxyl groups.
  • 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 dissolved by the dissolution of the metal surface. Ions are generated, metal ions are generated from the surface of the ceramic layer 2, the metal ions and the functional groups on the surface of the ceramic layer 2 (functional groups generated by making the ceramic layer 2 surface porous), and surface stabilization
  • a functional group such as a carboxyl group or a hydroxyl group in the agent (substance for forming the protective film) is bonded to form a protective film on the surface of the ceramic layer 2 in the same manner, but the active exposed surface of the internal electrode 3 is uniform. As a result of the denser protective film being formed by such an electric double layer, it becomes difficult to form an oxide film on the entire intermediate product 40 of the multilayer ceramic capacitor.
  • 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, so that even if it is taken out from the treatment aqueous solution and touched with air, There is no immediate formation of an oxide film on the active surface.
  • the functional group is bonded toward the ceramic layer 2 side and the internal electrode 3 side, while the organic group is directed outward.
  • the surface of the intermediate product 1 is resin-coated or the intermediate product 1 is molded with a sealing resin, the affinity between the resin and the organic group is extremely high, and the adhesion with the intermediate product 1 is extremely high. Since it is high, an extremely excellent sealing effect can be obtained.
  • external electrodes 5 are formed at both ends or a plurality of locations on the side surface to manufacture the multilayer ceramic capacitor of the present invention.
  • the protective film is volatilized / decomposed, or baked / carbon dioxide gas, so that the conductivity between the internal electrode 3 and the external electrode 5 is completely adversely affected. There is nothing.
  • an organic acid or a surfactant may be added to the treatment aqueous solution containing the halogen 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.
  • the organic acid an excess of the intermediate product 40 is used. There is no particular limitation as long as it is possible to prevent such etching.
  • this organic acid an organic acid having a carboxyl group (—COOH) in the molecule is generally preferred, and a monocarboxylic acid, dicarboxylic acid, tricarboxylic acid, polyoxymonocarboxylic acid, polyoxydicarboxylic acid or polyoxytricarboxylic acid is preferred.
  • Examples of the acid 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 to be added is appropriately determined depending on the material of the intermediate product 1 of the multilayer ceramic capacitor, which is the object, the kind and concentration of the inorganic acid used, and is not particularly limited. In general, it is preferably in the range of 0.005 to 10.0% by weight, 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.
  • the addition amount of the organic acid is less than 0.005% by weight based on the entire treatment aqueous solution containing the halogen-based compound, its action and effect are insufficient, and the required suppression effect cannot be obtained. If the amount exceeds 10.0% by weight with respect to the entire treatment aqueous solution, the effect is limited, meaning that not only is meaningless, but also the balance and adjustment with other components become worse, and it becomes uneconomical. It is not preferable.
  • organic acids may be added by mixing not only one type but also two or more types as appropriate.
  • the “surfactant” is added mainly for the purpose of achieving uniform treatment or developing gloss by infiltrating and adapting the treatment aqueous solution containing the halogen compound to the details of the intermediate product 1 of the multilayer ceramic capacitor.
  • Any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a nonionic surfactant can be used.
  • the anionic surfactant includes fatty acid salt type, alkylbenzene sulfonate type, alkyl sulfate ester type, linear secondary sulfonate type, dialkyl sulfosuccinate type, POE alkyl or alkylphenyl ether.
  • fatty acid salt type alkylbenzene sulfonate type, alkyl sulfate ester type, linear secondary sulfonate type, dialkyl sulfosuccinate type, POE alkyl or alkylphenyl ether.
  • examples thereof include a sulfate ester salt type and a POE alkyl or alkylphenyl ether phosphate ester salt type.
  • examples of the cationic surfactant include alkylpicolinium chloride type, alkyltriethylammonium chloride type, and other quaternary ammonium salt types.
  • Nonionic surfactants include 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.
  • amphoteric surfactants include alkylcarboxybetaine type, alkylaminocarboxylic acid type and alkylimidazoline type.
  • nonionic surfactants include POE alkyl ether, POE alkyl phenyl ether, sucrose fatty acid ester, ethylene glycol, and glycerin.
  • the amount of these surfactants to be added is appropriately determined depending on the material of the intermediate product 1 of the multilayer ceramic capacitor that is the target, the kind and concentration of the inorganic acid, and is not particularly limited. In general, it is preferably in the range of 0.0005 to 5.0% by weight, more preferably in the range of 0.001 to 1.5% by weight, based on the entire treatment aqueous solution containing the halogen compound. A range of 05 to 1.0% by weight is particularly preferred.
  • the addition amount of the surfactant is less than 0.0005% by weight with respect to the entire treatment aqueous solution, the addition amount of the surfactant is too small to obtain the required addition effect, whereas 5.0% by weight.
  • Exceeding not only is meaningless because the effect is limited, so that the treatment aqueous solution containing the halogen-based compound and the waste solution thereof are foamed to make the treatment and handleability difficult, and it is not preferable.
  • the surfactant may be added as a mixture of not only one type but also two or more types.
  • the intermediate product 1 of the multilayer ceramic capacitor of the present invention is manufactured by the manufacturing method of the intermediate product 1 of the multilayer ceramic capacitor of the present invention.
  • the multilayer ceramic capacitor 10 of the present invention uses the intermediate product 1 of the multilayer ceramic capacitor of the present invention.
  • the external electrode 5 is applied to the internal electrode 3 by a known method, for example, at a plurality of positions on both ends or side surfaces thereof. Manufactured by electrical connection.
  • Electrode 5 is a known method for applying / baking conductive paste, dipping / baking conductive paste, printing / baking conductive paste, and jetting conductive ink containing metal powder in the form of a mist from a nozzle. It may be formed by printing / baking by a method, spraying / baking of a conductive paste containing metal powder, or metal vapor deposition, plating or sputtering.
  • the intermediate product 1 of the multilayer ceramic capacitor of the present invention is used, and external electrodes 5 are formed in the intermediate product 1 so as to be electrically connected to the internal electrodes 3 at both ends or side surfaces.
  • the metal material of the external electrode 5 the same material as that of the internal electrode 3 can be used, and a glass such as B 2 O 3 —SiO 2 —BaO glass or Li 2 O—SiO 2 —BaO glass is used as these metal materials. You may use what added the frit.
  • the internal electrode 3 is made of a conductive paste containing glass frit and copper powder. It is applied to both ends of the exposed intermediate product 1 of the multilayer ceramic capacitor, and is baked in a vacuum firing furnace to form an inner external electrode 5a that directly contacts 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 the glass frit and the metal powder entering the porous portion 2a at both ends of the ceramic layer 2 to be firmly integrated. .
  • a first plated layer 5b made of nickel or the like is formed on the external electrode 5a, and a second plated layer 5c made of solder, tin or the like is further formed on the plated layer 5b, so that the laminated ceramic of the present invention is formed.
  • the capacitor 10 is manufactured.
  • the first and second plated layers 5b and 5c described above may be omitted depending on the use of the multilayer ceramic capacitor 10 of the present invention.
  • the connection and adhesion between the internal electrode 3 and the external electrode 5 are extremely improved, so that the quality is stable and the dielectric is excellent. It has characteristics.
  • 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.
  • the present invention as shown in the examples described later, it is performed by a simple process in which at least an end portion of the intermediate product 40 of the fired multilayer ceramic capacitor is brought into contact with a treatment aqueous solution containing a halogen compound for a short time. Therefore, productivity can be remarkably improved. Unlike the conventional physical processing using a special dedicated jig, in the present invention, the product quality is stabilized, the defect occurrence rate is low, the yield is improved, and the production cost is reduced. The technical problems of the present invention can be solved at once, such as a significant reduction.
  • Test piece A laminated body formed by laminating 300 green sheets using BaTiO3 as the ceramic layer 2 and Ni as the internal electrode 3 and bonding the green sheet is 3.15 mm in length, 1.60 mm in width, and thickness
  • the intermediate product 4 of the multilayer ceramic capacitor was manufactured by cutting into a 1.60 mm rectangular parallelepiped shape. This intermediate product 4 was fired to produce an intermediate product 40 of a 300-layer laminated ceramic capacitor serving 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. 117 before being processed.
  • Treatment aqueous solution containing a halogen compound A treatment aqueous solution containing a halogen compound of each composition shown in Tables 1 to 6 was prepared.
  • each example was produced with 1000 pieces, and 20 pieces were arbitrarily taken out from the intermediate product 40 of each multilayer ceramic capacitor, and the same processing was performed.
  • 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.
  • those that can be evaluated in the same manner are ⁇ when 90% or more, ⁇ when less than 90% and 80% or more, The case of less than 80% and 60% or more was evaluated as ⁇ .
  • the intermediate product 40 of the multilayer ceramic capacitor is the end face of the internal electrode 3 embedded in the ceramic layer 2 by the etching treatment of the treatment aqueous solution containing the halogen compound.
  • the end portion can be efficiently exposed or protruded outward in a short time.
  • the end face or the end of the internal electrode 3 can be exposed or projected outward with a very high probability, so that the book of excellent quality It was confirmed that the intermediate product 1 of the multilayer ceramic capacitor of the invention can be obtained.
  • a Cu paste containing glass frit is applied to the end portion 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 a Cu electrode 5a as a base electrode.
  • the Ni-plated electrode 5b and the Sn-plated electrode 5c are sequentially stacked from the top, and the external electrode 5 is attached to complete the multilayer ceramic capacitor 10 of the present invention.
  • the present invention is not limited to the production of the multilayer ceramic capacitor of the present invention and the production of the multilayer ceramic capacitor of the present invention, and is configured by forming external electrodes at the end of various ceramic intermediate products having internal electrodes.
  • the present invention can also be applied to the manufacture of various types of electronic components, and specifically, for example, can also be applied to the manufacture of chip-type inductors, chip-type LC components, chip-type arrays, and the like.

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Abstract

L'invention aborde le problème de la réalisation d'un procédé de production d'un produit intermédiaire d'un condensateur céramique multicouche qui est capable d'augmenter remarquablement la productivité tout en ayant un rendement extrêmement élevé, ledit produit intermédiaire étant stable et hautement fiable tout en présentant une excellente adhérence entre une électrode interne et une électrode externe et des qualités élevées telles de très bonnes caractéristiques électriques ; d'une solution de traitement aqueuse contenant un composé d'halogène qui est utilisée pour la production d'un produit intermédiaire d'un condensateur céramique multicouche ; d'un produit intermédiaire d'un condensateur céramique multicouche ; d'un procédé de fabrication d'un condensateur céramique multicouche ; et d'un condensateur céramique multicouche. Selon l'invention, lorsqu'un produit intermédiaire (1) d'un condensateur céramique multicouche est produit, après obtention d'un produit intermédiaire (4) d'un condensateur céramique multicouche par liaison par compression et coupe d'un stratifié qui est obtenu par stratification en alternance d'une pluralité de couches de céramique (2) et d'une pluralité d'électrodes internes (3), le produit intermédiaire (4) est soumis à une cuisson et ensuite une solution de traitement aqueuse contenant un composé d'halogène est mise en contact avec au moins une portion d'extrémité d'un produit intermédiaire (40) d'un condensateur céramique multicouche après cuisson, gravant ainsi les portions d'extrémité des couches de céramique (2) de sorte que les surfaces d'extrémité ou les portions d'extrémité des électrodes internes (3) enfouies dans les couches de céramique (2) soient exposées à l'extérieur depuis les surfaces d'extrémité des couches de céramique (2). Une solution de traitement aqueuse contenant un composé d'halogène est utilisée à cette occasion. Un condensateur céramique multicouche (10) est obtenu en produisant des électrodes externes (5) sur les deux portions d'extrémité ou sur une pluralité de positions de la surface latérale du produit intermédiaire (1) ainsi obtenu d'un condensateur céramique multicouche, de telle manière que les électrodes externes (5) sont électriquement connectées aux électrodes internes.
PCT/JP2015/086191 2015-01-16 2015-12-25 Procédé de production d'un produit intermédiaire de condensateur céramique multicouche, solution de traitement aqueuse contenant un composé d'halogène utilisé pour la production d'un produit intermédiaire de condensateur céramique multicouche, produit intermédiaire de condensateur céramique multicouche, procédé de fabrication d'un condensateur céramique multicouche et condensateur céramique multicouche WO2016114091A1 (fr)

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