JP3921177B2 - Composite electronic components - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a composite electronic component, and more particularly to a CR composite electronic component in which a resistor is added to a multilayer ceramic capacitor.
[0002]
[Prior art]
[Patent Document 1]
JP-A-5-166672
[Patent Document 2]
JP-A-6-333781
Multilayer ceramic electronic components such as capacitors, inductors, thermistors, and varistors are used in various electronic devices because of their small volume, robustness, and high reliability. As electronic devices become smaller, they become even smaller. There is a need for higher performance and higher performance. Among such multilayer ceramic electronic components, for example, a multilayer ceramic capacitor usually includes a laminate in which dielectric layers and internal electrode layers are alternately laminated, and a pair of side surfaces provided on opposite sides of the laminate. The structure includes an external electrode. Such a multilayer ceramic capacitor is used, for example, as a smoothing capacitor constituting an output smoothing circuit.
[0003]
However, the multilayer ceramic capacitor has a problem that an equivalent series resistance (ESR) is very low, a signal in the circuit loops and an oscillation phenomenon occurs, resulting in noise. That is, when a multilayer ceramic capacitor having a low ESR is used as the smoothing capacitor, the secondary side smoothing circuit is equivalently composed of only the L and C components, and the phase components existing in the circuit are ± 90 ° and 0 It becomes only °, and it oscillates easily with no phase margin.
[0004]
For this reason, various composite electronic components in which a resistance component is added to the multilayer ceramic capacitor to increase the ESR have been proposed. For example, of the connection between a pair of external electrodes and an internal electrode layer, one external electrode is first connected by an electrode pad disposed on the side surface of the laminate, and then this electrode pad and the external electrode A composite electronic component having a structure in which an electrode is connected via a resistor disposed on a side surface of a laminate is disclosed (Patent Document 1). In the composite electronic component having such a structure, the current supplied to one of the external electrodes is sent to the internal electrode via a resistor disposed outside the laminated body.
Also disclosed is a composite electronic component having a structure in which one of a pair of external electrodes connected to an internal electrode layer is connected to an external conductor layer provided at the center of a side surface of a multilayer body via a resistor (Patent Document 2). . In the composite electronic component having such a structure, the current supplied to the external conductor layer is sent to the external electrode via a resistor disposed outside the multilayer body.
[0005]
[Problems to be solved by the invention]
However, in the composite electronic component as described above, the resistance disposed on the side surface of the laminate is very close to or in contact with the external electrode, so that the resistance is deteriorated by heat when soldering the external electrode. There is a problem that the resistance value is changed due to adhesion of solder on the resistor and the resistance value is changed, and a desired resistance value cannot be obtained. Furthermore, the composite electronic component disclosed in Patent Document 2 has a problem that the external conductor layer that is a substantial external electrode is small and the mountability is poor.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composite electronic component that is easy to adjust the resistance value and has high mountability and reliability.
[0006]
[Means for Solving the Problems]
  In order to solve such an object, the present invention includes a laminate in which a plurality of internal electrode layers are laminated via a dielectric layer, and a pair of external electrodes provided on opposite end surfaces of the laminate. In the composite electronic component, the internal electrode layer includes a first internal electrode layer and a second internal electrode layer that are alternately stacked via a dielectric layer, and excludes at least one of the plurality of first internal electrode layers. A layer is pulled out to one end face of the laminate and connected to one external electrode;At least one of the first internal electrode layers connected to the external electrode is divided into an electrically insulated outer internal electrode layer and an inner internal electrode layer, and only the outer internal electrode layer is the laminate. Is pulled out to one end face of the first electrode and connected to the external electrode, and the area of the outer internal electrode layer is smaller than the area of the inner internal electrode layer,The plurality of second internal electrode layers are drawn out to the other end face of the laminate and connected to the other external electrode,Including the outer internal electrode layer and the inner internal electrode layerEach first internal electrode layer has a protruding portion exposed on the side surface of the laminate, and among the protruding portions,An exposed surface of the protruding portion of the inner internal electrode layer;The exposed surface of the protruding portion of the first internal electrode layer that is not connected to the external electrode is connected by a connecting member disposed on the side surface, and is connected to the external electrode.The outer internal electrode layerConnect the protruding part of the connector and the connecting memberThe resistor is disposed on the side surface, and the resistor is in a non-contact state with the pair of external electrodes.The configuration is as follows.
[0007]
  In the present invention, the resistor is located at a position connecting the first internal electrode layer connected to the external electrode and the other first internal electrode layer, and is separated from the external electrode. It is difficult to be affected by heat at the time of soldering the electrode, and the solder is difficult to adhere.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below.
FIG. 1 is a perspective view showing an embodiment of a composite electronic component of the present invention, and FIG. 2 is a cross-sectional view taken along line AA of the composite potential component shown in FIG.
As shown in FIGS. 1 and 2, the composite electronic component 1 of the present invention includes a laminate 2 in which first internal electrode layers 6 and second internal electrode layers 7 are alternately laminated via dielectric layers 9. A pair of external electrodes 3 and 4 provided on opposite end surfaces of the laminate 2 and a resistor 5 provided on the side surface 2a of the laminate 2 where the external electrodes 3 and 4 are not provided. ing. The laminated body 2 is usually a rectangular parallelepiped shape, but the shape is not particularly limited. Moreover, the dimension of the laminated body 2 is not particularly limited, and can be appropriately set according to the application. For example, (0.6 to 5.6 mm) × (0.3 to 5.0 mm) × (0.3 About 2.5 mm).
[0009]
In the composite electronic component 1 of the present invention, the resistor 5 is in a state of being separated from the external electrodes 3 and 4. In addition, among the plurality of first internal electrode layers 6, the first internal electrode layer 6 positioned on the most surface side of the multilayer body 2 is drawn out to one end face of the multilayer body 2 to form one external electrode 3. The other first internal electrode layers 6 are connected and are not connected to any of the external electrodes 3 and 4. The second internal electrode layer 7 is drawn to the other end face of the multilayer body and connected to the other external electrode 4.
[0010]
FIG. 3 is a perspective view showing a state in which the external electrodes 3 and 4 and the resistor 5 are removed from the composite electronic component 1, and FIG. 4 shows only the first internal electrode layer 6 and the second internal electrode layer 7 extracted. FIG. As shown in FIGS. 3 and 4, among the plurality of first internal electrode layers 6, the first internal electrode layer 6 located on the most surface side of the multilayer body 2 is drawn to the end surface 2 b of the multilayer body 2. It is. Each first internal electrode layer 6 has protrusions 6a and 6b exposed on the side surface 2a of the laminate 2 where the external electrodes 3 and 4 are not provided. And the exposed surface of the protrusion part 6a of the 1st internal electrode layer 6 connected to the external electrode 3 is connected to the connection member 8a arrange | positioned at the side surface 2a of the laminated body 2, and is not connected to the external electrode 3. The exposed surface of the protrusion 6 b of the first internal electrode layer 6 is connected by a connection member 8 b disposed on the side surface 2 a of the multilayer body 2. In the present invention, the resistor 5 is disposed on the side surface 2a so as to connect the protruding portion 6a (connecting member 8a) of the first internal electrode layer 6 connected to the external electrode 3 and the connecting member 8b. .
The distance between the exposed surface of the protrusion 6a and the exposed surfaces of the plurality of protrusions 6b, and the size and distance of the connection members 8a and 8b, together with the material used, the thickness, and the like of the resistor 5, are as follows. It is an element that determines the resistance value and can be designed as appropriate.
[0011]
The composite electronic component 1 of the present invention as described above is in a position where the resistor 5 is connected to the first internal electrode layer 6 connected to the external electrode 3 and the other first internal electrode layer 6, and the external Since the electrodes 3 and 4 are in a state of being separated from each other, they are not easily affected by heat when soldering the external electrodes 3 and 4, and the deterioration of the resistor due to heat is prevented. In addition, the external electrodes 3 and 4 and the resistor 5 are connected when the external electrodes 3 and 4 are soldered as compared with the case where the external electrodes 3 and 4 are routed on the surface of the electronic component and the resistors are connected on a predetermined surface. Therefore, a desired resistance value can be obtained. Furthermore, it is not necessary to incorporate a resistor in the laminated body 2 and the manufacturing is easy, and the resistance value can be easily adjusted by variously selecting the resistor 5 to be used.
[0012]
FIG. 5 is a cross-sectional view corresponding to FIG. 2 showing another embodiment of the composite electronic component of the present invention, and FIG. 6 is a diagram showing a state where external electrodes and resistors are removed from the composite electronic component shown in FIG. FIG. 7 is a perspective view corresponding to FIG. 4 showing a state in which only the first internal electrode layer and the second internal electrode layer are extracted.
As shown in FIGS. 5 to 7, the composite electronic component 11 according to the present invention includes a laminated body 12 in which first internal electrode layers 16 and second internal electrode layers 17 are alternately laminated with dielectric layers 19 interposed therebetween. A pair of external electrodes 13 and 14 provided on the opposing end surface 12b of the laminated body 12, and a resistor 15 (disposed on the side surface 12a of the laminated body 12 where the external electrodes 13 and 14 are not provided. 2). The first internal electrode layer 16 connected to the external electrode 13 is divided into an electrically insulated outer internal electrode layer 16 ′ and an inner internal electrode layer 16 ″, and only the outer internal electrode layer 16 ′. Is pulled out to the end face 12 b of the laminated body 12 and connected to the external electrode 13.
[0013]
The outer internal electrode layer 16 ′, the inner internal electrode layer 16 ″, and the other first internal electrode layers 16 constituting the first internal electrode layer 16 are laminated bodies in which the external electrodes 13 and 14 are not provided. 12 have protrusions 16'a, 16 "a, 16b exposed on the side surface 12a. The exposed surface of the protrusion 16 ′ a of the outer internal electrode layer 16 ′ connected to the external electrode 3 is connected to a connection member 18 a disposed on the side surface 12 a of the multilayer body 12. On the other hand, the exposed surfaces of the protrusions 16 ″ a of the inner internal electrode layer 16 ″ that are not connected to the external electrode 13 and the protrusions 16b of the plurality of first internal electrode layers 16 are connected to the side surface 12a of the laminate 12. The members 18b are connected to each other. In the present invention, the resistor 15 is disposed on the side surface 12a so as to connect the protrusion 16'a (connecting member 18a) of the outer internal electrode layer 16 'connected to the external electrode 13 and the connecting member 18b. ing.
[0014]
The distance between the protrusion 16′a and the plurality of protrusions 16 ″ a and 16b and the size and distance of the connection members 18a and 18b are determined by the resistance value of the composite electronic component 11 together with the material used, the thickness, and the like of the resistor 15. Can be designed as appropriate.
In such a composite electronic component 11, the first internal electrode layer 16 connected to the external electrode 13 is divided into two, an outer internal electrode layer 16 ′ and an inner internal electrode layer 16 ″. Since "" can act as an internal electrode layer constituting the multilayer capacitor, it has a higher capacitance than the above-described composite electronic component.
[0015]
Further, in the present invention, the division ratio of the first internal electrode layer 16 divided into the outer internal electrode layer 16 ′ and the inner internal electrode layer 16 ″, that is, the outer internal electrode layer 16 ′ and the inner internal electrode layer 16 ″. The capacitance can be further improved by setting the area ratio to a smaller one, for example, 1/2 or less. FIG. 8 is a perspective view showing the first internal electrode layer and the second internal electrode layer when the area ratio between the external internal electrode layer 16 ′ and the internal internal electrode layer 16 ″ is smaller than the example shown in FIG. In the present invention, the protrusion 16′a of the outer internal electrode layer 16 ′ and the protrusion 16 ″ a of the inner internal electrode layer 16 ″ may be exposed to the side surface 12a of the multilayer body 12. There is no particular limitation on the shape of the two divided inner electrode layers 16 ′ and inner electrode layers 16 ″.
[0016]
In the above-described composite electronic component of the present invention, the first internal electrode layers 6 and 16 (outer internal electrode layers) are drawn to the end faces 2b and 12b of the multilayer bodies 2 and 12 and connected to one of the external electrodes 3 and 13. 16 ') is located on the most surface side of the multilayer bodies 2 and 12 among the plurality of first internal electrode layers 6 and 16, but is not limited thereto. For example, among the plurality of first internal electrode layers 6 and 16, the structure of the first internal electrode layers 6 and 16 located substantially in the center is connected to the external electrodes 3 and 13 and the resistors 5 and 15. It is good also as the above-mentioned structure. The first internal electrode layers 6 and 16 (outer internal electrode layers 16 ') that are drawn out to the end faces 2b and 12b of the multilayer bodies 2 and 12 and are connected to one of the external electrodes 3 and 13 include a plurality of first internal electrodes. There may be two or more electrode layers 6 and 16 (excluding at least one layer).
[0017]
In the present invention, the resistors 5 and 15 are directly connected to the exposed surface of the protruding portion 6a of the first internal electrode layer 6 and the protruding portion 16 'of the outer internal electrode layer 16' without using the connecting member 8a or the connecting member 18a. It may be connected to the exposed surface of a.
In the above-described composite electronic component of the present invention, the number of internal electrode layers is an example, and the present invention is not limited to this.
[0018]
Next, members constituting the composite electronic component of the present invention will be described.
The external electrode constituting the composite electronic component of the present invention can use at least one metal such as Pd, Ag, Au, Cu, Pt, Rh, Ru, Ir, or an alloy thereof as a conductive material. . The thickness of the external electrode is not particularly limited, and can be, for example, about 1 to 100 μm, particularly about 5 to 50 μm.
Further, the external electrode may contain glass for the purpose of improving the sinterability of the conductive material and ensuring the adhesion with the laminate.
[0019]
The conductive material used for the internal electrode layer constituting the composite electronic component of the present invention is not particularly limited, but by using a material having reduction resistance as the constituent material of the dielectric layer, an inexpensive base metal is used. Can do. The base metal used as the conductive material is preferably Ni or a Ni alloy, for example. The Ni alloy is preferably an alloy of Ni and one or more of Mn, Cr, Co, Al, etc., and the Ni content in the alloy is preferably 95% by weight or more. Moreover, in Ni or Ni alloy, various trace components, such as P, may be contained in an amount of about 0.1% by weight or less. The thickness of the internal electrode layer can be appropriately set according to the use of the composite electronic component, and can be set to, for example, about 0.5 to 5 μm, particularly about 0.5 to 2.5 μm.
[0020]
The resistor constituting the composite electronic component of the present invention is formed of a material containing a conductive oxide and an insulating oxide. The conductive oxide is not particularly limited, and preferably contains at least one of ruthenium oxide, a ruthenium oxide compound, and graphite, for example. Examples of ruthenium oxide include RuO.₂, Bi₂Ru₂O₇, SrRuO_Three, CaRuO_Three, Pb₂Ru₂O₆, BaRuO_ThreeEtc. Moreover, as graphite, graphite carbon can be used.
The insulating oxide is not particularly limited, but it is preferable to select glass in order to control the resistance value, ensure sinterability with the conductive material, and adherence with the connection member. The composition of the glass is not particularly limited, and can be appropriately set in consideration of ease of control of the resistance value and required characteristics.
[0021]
In addition, a metal oxide can be added to the resistor in order to adjust the resistance value or to control electrical characteristics required for other resistors. Furthermore, when a resistance of 0.1Ω or less is required, the resistor may be composed of a metal and an insulating oxide.
The resistance value of the resistor can be controlled by adjusting the mixing ratio of the conductive oxide and the insulating oxide, and the resistance value can also be controlled by the thickness of the resistor.
Moreover, you may coat | cover a resistor using insulators, such as glass and resin, as needed. Further, a resin-based material can be used as the resistor, and in this case, the conductive material is not particularly limited, but for example, carbon is preferably used.
[0022]
There is no restriction | limiting in particular as a dielectric material used for the dielectric material layer which comprises the composite electronic component of this invention, A various dielectric material can be used. For example, titanium oxide-based, titanic acid-based composite oxide, or a mixture thereof can be used. Titanium oxide includes NiO, CuO, Mn as required_ThreeO_Four, Al₂O_Three, MgO, SiO₂Etc. in the range of about 0.001 to 30% by weight in total₂Etc. In addition, as the titanate-based composite oxide, barium titanate (BaTiO_Three) And the like. The atomic ratio of Ba / Ti is preferably in the range of 0.95 to 1.20. For barium titanate, MgO, CaO, Mn_ThreeO_Four, Y₂O_Three, V₂O_Five, ZnO, ZrO₂, Nb₂O_Five, Cr₂O_Three, Fe₂O_Three, P₂O_Five, SrO, Na₂O, K₂O etc. may be contained in the range of about 0.001 to 30% by weight in total. In addition, for the adjustment of the firing temperature and the linear expansion coefficient, (BaCa) SiO_ThreeGlass such as glass may be contained.
[0023]
The thickness per layer of the dielectric layer is not particularly limited, but can be set to about 0.5 to 20 μm, for example. In addition, the number of laminated dielectric layers can usually be about 2 to 300.
The connecting member constituting the composite electronic component of the present invention can use at least one metal such as Pd, Ag, Au, Cu, Pt, Rh, Ru, Ir, or an alloy thereof as a conductive material. .
Further, the connection member may contain glass for the purpose of improving the sinterability of the conductive material and ensuring the adhesion with the laminate or the resistor.
The thickness in particular of a connection member is not restrict | limited, For example, it can be set as 0.5-30 micrometers, especially about 5-20 micrometers.
[0024]
In the composite electronic component of the present invention, for example, first, a green chip body is produced by a normal printing method or sheet method using a paste to obtain a laminated body. Next, the external electrode paste is applied to the opposing end faces (the surface where the first internal electrode layer is drawn and exposed, and the surface where each second internal electrode layer is drawn and exposed) of this laminate. Printing or transferring, and printing or transferring the connecting member paste so as to connect the protruding portions of the plurality of first internal electrode layers (layers not connected to the external electrodes) exposed on the side surface of the laminate; The connection member paste is printed or transferred so as to connect the protrusions of the first internal electrode layer (layer connected to the external electrode) exposed on the side surface of the laminate, and then fired to form the external electrode. A connecting member is formed. Next, the resistor paste can be printed or transferred so as to cover the connection member, and then fired.
[0025]
<Dielectric layer paste>
As the dielectric layer paste, a material obtained by kneading and dispersing a dielectric material and an organic vehicle can be used.
The composition of the dielectric material can be appropriately selected in consideration of the application of the composite electronic component to be manufactured. For example, when barium titanate is used as the titanate-based composite oxide, BaTiO synthesized by a hydrothermal synthesis method or the like._ThreeIn addition, a method of mixing the subcomponent raw materials can be used. BaCO_ThreeAnd TiO₂A dry synthesis method may be used in which a mixture of bismuth and subcomponents is calcined and subjected to a solid phase reaction, or a hydrothermal synthesis method may be used. Further, a mixture of a precipitate obtained by a coprecipitation method, a sol-gel method, an alkali hydrolysis method, a precipitation mixing method, and the like and a subcomponent raw material may be preliminarily calcined and synthesized. In addition, at least 1 sort (s), such as an oxide and various compounds which become an oxide by baking, for example, carbonate, an oxalate, nitrate, a hydroxide, an organic metal compound, etc., can be used for a subcomponent raw material.
[0026]
The average particle size of the dielectric material can be determined according to the average crystal particle size of the target dielectric layer, and usually a powder having an average particle size of about 0.1 to 5 μm is used. Further, the content of the dielectric material in the dielectric layer paste is usually about 30 to 80% by weight.
The organic vehicle used for the dielectric layer paste is obtained by dissolving a binder in an organic solvent. As the binder, for example, known resin binders such as ethyl cellulose, a copolymer of polyvinyl butyral and methacrylic acid ester, and an acrylic acid ester-based copolymer can be used. Moreover, organic solvents, such as terpineol, a butyl carbitol, acetone, toluene, can be used as an organic solvent for melt | dissolving a binder. The content of the binder or the organic solvent in the dielectric layer paste is not particularly limited, and can usually be about 1 to 5% by weight for the binder and about 10 to 50% by weight for the organic solvent.
[0027]
<Internal electrode layer paste>
The internal electrode layer paste is prepared by kneading and dispersing the above-mentioned various conductive metals and alloys, or various oxides, organometallic compounds, etc. that become the above-mentioned conductive materials after firing, and the above-described organic vehicle. Prepare.
[0028]
<Paste for external electrode and connection member>
The paste for external electrodes and connection members uses at least one metal such as Pd, Ag, Au, Cu, Pt, Rh, Ru, Ir, or an alloy thereof as a conductive material, and the above internal electrode layer It is prepared in the same way as the paste.
The various pastes described above may contain additives selected from various dispersants, plasticizers, dielectrics, insulators, and the like as necessary. The total content of these is preferably 10% by weight or less.
[0029]
<Resistor paste>
The resistor paste is prepared by kneading and dispersing the above-mentioned various conductive oxides and insulating oxides and the above organic vehicle.
[0030]
[Production of green chip body]
When using the printing method, the dielectric layer paste and the internal electrode layer paste are laminated and printed on a support such as polyethylene terephthalate. At this time, the first internal electrode layer is printed so that the end portion of the internal electrode layer paste is not exposed from the end portion of the dielectric layer paste except for the protruding portion, and is connected to the external electrode. Only the layer is printed so that the lead-out to the external electrode side and the protrusion are exposed from the end of the dielectric layer paste. Further, the second internal electrode layer is printed so that the lead to the external electrode side of the internal electrode layer paste is exposed from the end portion of the dielectric layer paste. After laminating and printing in this way, it is cut into a predetermined shape to form a chip, and peeled from the support to form a green chip body.
In the case of using the sheet method, a green sheet is formed using a dielectric layer paste, and a printed material similar to the above using an internal electrode layer paste is laminated, cut into a predetermined shape, and green chips Let it be the body.
[0031]
[Binder removal process]
The green chip body produced as described above is preferably subjected to binder removal treatment before firing. The conditions for this binder removal treatment can be set as appropriate in consideration of the materials used. For example, when a base metal such as Ni or Ni alloy is used for the conductive material of the internal electrode layer, the conditions are as follows. Is preferred.
Debinding conditions
Temperature increase rate: 5 to 300 ° C./hour, particularly 10 to 100 ° C./hour
Holding temperature: 200-400 ° C, especially 250-300 ° C
Temperature holding time: 0.5 to 24 hours, especially 5 to 20 hours
Atmosphere: In the air
[0032]
[Baking process]
The firing of the green chip body can be appropriately set in consideration of the dielectric material in the dielectric paste, the type of the electrode material in the internal electrode layer paste, etc. When a base metal such as Ni or Ni alloy is used, the firing atmosphere is N₂As the main component and H₂H obtained by water vapor pressure at 1 to 10% by volume and 10 to 35 ° C.₂What mixed O gas is preferable. The oxygen partial pressure is 10^-3-10^-8Pa is preferable. When the oxygen partial pressure is less than the above range, the conductive material of the internal electrode layer may be abnormally sintered and may be interrupted. Further, when the oxygen partial pressure exceeds the above range, the internal electrode layer may be oxidized.
The temperature during firing is preferably 1100 to 1400 ° C, particularly preferably 1200 to 1300 ° C. If the holding temperature is less than 1100 ° C., the densification is insufficient, and if it exceeds 1400 ° C., the internal electrode layer tends to break. The temperature holding time during firing is preferably 0.5 to 8 hours, particularly 1 to 3 hours.
[0033]
[Annealing process]
When firing in a reducing atmosphere, it is preferable to anneal the laminate. Annealing is a process for re-oxidizing the dielectric layer, and this can significantly increase the accelerated life of the insulation resistance.
The oxygen partial pressure in the annealing atmosphere is 10^-3Pa or more, especially 10^-3-10^-1Pa is preferable. When the oxygen partial pressure is less than the above range, it is difficult to reoxidize the dielectric layer, and when the oxygen partial pressure exceeds the above range, the internal electrode layer may be oxidized.
[0034]
The annealing holding temperature is preferably 1100 ° C. or lower, particularly 500 to 1000 ° C. When the holding temperature is less than 500 ° C., the re-oxidation of the dielectric layer becomes insufficient, the accelerated life of the insulation resistance is shortened, and when it exceeds 1100 ° C., the internal electrode layer is oxidized and the capacitance is reduced. It reacts with the dielectric substrate and shortens the accelerated life. Note that the annealing step may be composed of only temperature rise and temperature drop. In this case, it is not necessary to take a temperature holding time, and the holding temperature is synonymous with the maximum temperature. The temperature holding time is preferably 0 to 20 hours, particularly 2 to 10 hours. N as the atmosphere gas₂And humidified H₂It is preferable to use a gas.
In each process of the above binder removal, firing, and annealing, N₂, H₂For example, a wetter or the like can be used to humidify the mixed gas or the like. The water temperature in this case is preferably about 5 to 75 ° C.
[0035]
The steps of removing the binder, firing, and annealing may be performed continuously or independently. When these steps are performed continuously, after removing the binder, the atmosphere is changed without cooling, and then the temperature is raised to the holding temperature for firing, followed by firing, followed by cooling and holding temperature in the annealing step. It is preferable to perform annealing by changing the atmosphere when the temperature reaches.
When these steps are performed independently, in the binder removal processing step, the temperature is raised to a predetermined holding temperature, held for a predetermined time, and then lowered to room temperature. At that time, the binder removal atmosphere is the same as in the case of continuous operation. Further, in the annealing step, the temperature is raised to a predetermined holding temperature, held for a predetermined time, and then lowered to room temperature. The annealing atmosphere at that time is the same as in the case where the annealing is continuously performed. Alternatively, the binder removal step and the firing step may be performed continuously and only the annealing step may be performed independently, or only the binder removal step may be performed independently and the firing step and the annealing step performed continuously. You may go.
[0036]
[Formation of external electrodes and connecting members]
Opposing end faces of the chip body (laminated body) produced as described above (the surface on which the first internal electrode layers are drawn and exposed, and the surface on which each second internal electrode layer is drawn and exposed) Print or transfer external electrode paste. Further, the connection member paste is printed or transferred so as to connect a plurality of protrusions of the first internal electrode layer (a layer not connected to the external electrode layer) exposed on the side surface of the laminate, The connection member paste is printed or transferred so as to connect the protruding portion of the first internal electrode layer (layer connected to the external electrode) exposed on the side surface, and then fired to connect the external electrode and the connection member. Form. The firing conditions of the external electrode paste and the connection member paste are, for example, N₂And H₂In a reducing atmosphere such as a mixed gas, it is preferable that the temperature is 600 to 800 ° C. for 10 minutes to 1 hour.
[0037]
[Resistor formation]
In the chip body (laminate) in which the external electrode and the connection member are formed, the resistor paste is printed or transferred so as to cover the connection member and be separated from the external electrode, and then fired. Form. The firing condition of the resistor paste is preferably, for example, in the air at 600 to 1000 ° C. for 10 minutes to 1 hour.
The composite electronic component of the present invention manufactured as described above is provided with a lead wire if necessary, and is mounted and used on a printed circuit board by soldering or the like.
[0038]
【Example】
Next, the present invention will be described in more detail with specific examples.
[Preparation of paste for dielectric layer]
As the main raw material for the dielectric layer, BaCO_Three(Average particle size 2.0 μm) and TiO₂(Average particle size 2.0 μm) was prepared. The atomic ratio Ba / Ti was 1.00. For 100 parts by weight of the main raw material, BaTiO_Three5 parts by weight, MnCO_Three1 part by weight of MgCO_Three1 part by weight, Y₂O_Three2 parts by weight of (BaCa) SiO_Three3 parts by weight was added, wet-mixed with an underwater ball mill, and dried. The obtained mixed powder was calcined at 1250 ° C. for 2 hours. The calcined powder was pulverized with an underwater ball mill and dried. To 100 parts by weight of the obtained calcined powder, 5 parts by weight of an acrylic resin as an organic binder and 80 parts by weight of ethyl acetate as an organic solvent were added and mixed with a ball mill to obtain a dielectric layer paste.
[0039]
[Preparation of internal electrode layer paste]
An internal electrode layer paste was prepared by adding 100 parts by weight of Ni particles having an average particle size of 0.4 μm to 4 parts by weight of 8 parts by weight of ethyl cellulose resin dissolved in 92 parts by weight of terpineol, and kneading with three rolls. did.
[0040]
[Preparation of paste for external electrode layer (connection member)]
As a conductive material, a mixed powder of 30% by weight of Ag powder (average particle size: 5.0 μm) and 70% by weight of Pd powder (average particle size: 1.0 μm) is prepared. 2 parts by weight of acrylic resin, 18 parts by weight of terpineol and 5 parts by weight of zinc-based glass frit having an average particle size of 2.0 μm were added and kneaded with three rolls to prepare a paste for the external electrode layer (connection member). did.
[0041]
[Preparation of resistor paste]
As the conductive material, 44.4 parts by weight of RuO₂Powder (average particle size 0.2 μm), 52.0 parts by weight of Ca-based glass frit (average particle size 2.0 μm) as a glass material, and 3.6 parts by weight of CuO (average particle size 2. 0 μm), and 5.4 parts by weight of ethyl cellulose and 67.4 parts by weight of terpineol are added to 100 parts by weight of the mixed powder, and the mixture is kneaded with three rolls to obtain a resistor paste. Was prepared.
[0042]
[Formation of laminate]
A polyethylene terephthalate film having a thickness of 50 μm was used as a support, and the dielectric layer paste was applied onto the support by the doctor blade method and dried at 60 ° C. to form a dielectric green sheet having a thickness of 5 μm.
Next, the internal electrode layer paste was printed on the dielectric green sheet in a predetermined pattern by screen printing and dried at 80 ° C. to form an internal electrode paste layer having a thickness of 1 μm. In the formation of the internal electrode paste layer, the paste layer serving as the first internal electrode layer is connected to the external electrode with the end of the paste layer not exposed from the end of the dielectric green sheet except for the protruding portion. Only the paste layer serving as the first internal electrode layer has the lead-out to the external electrode side and the protruding portion exposed from the end of the dielectric green sheet. In addition, the paste layer serving as the second internal electrode layer is assumed to be exposed to the external electrode side from the end of the dielectric green sheet.
[0043]
Next, 100 dielectric green sheets on which a paste layer to be a first internal electrode layer is formed and 100 dielectric green sheets on which a paste layer to be a second internal electrode layer are formed are alternately stacked, and the uppermost layer A dielectric green sheet having a paste layer serving as a first internal electrode layer connected to an external electrode is laminated on a dielectric green sheet (a sheet on which a paste layer serving as a second internal electrode layer is formed). , Thermocompression bonding (120 ° C, 1 t / cm²Pressure time for 10 minutes). Thereafter, the laminated body after firing was cut to have a length of 2.0 mm × width 1.2 mm × thickness 1.2 mm to obtain a green chip body, and this green chip body was subjected to binder removal treatment under the following conditions. .
(Binder removal conditions)
Temperature increase rate: 30 ° C / hour
Holding temperature: 260 ° C
Temperature holding time: 8 hours
Atmosphere: In the air
[0044]
Next, the green chip body was fired and annealed under the following conditions to obtain a laminate.
(Baking conditions)
Holding temperature: 1300 ° C
Temperature holding time: 3 hours
Atmosphere: humidified N₂+ H₂(H₂: 3% by volume)
(Annealing conditions)
Holding temperature: 1000 ° C
Temperature holding time: 2 hours
Atmosphere: humidified H₂Partial pressure of oxygen containing gas 10^-2Pa atmosphere
[0045]
[Production of composite electronic components]
The end surface of the laminate obtained by the above firing (the surface where the first internal electrode layer connected to the external electrode is exposed, and the second internal electrode layer is exposed every other layer so as to face this surface) The outer electrode layer paste was applied to the two end faces and dried. Further, after polishing the side surface of the laminated body where the protruding portion of the first internal electrode layer is exposed by the sand blast method, the above connection is performed so as to cover the exposed surface of the protruding portion of the first internal electrode layer that is not connected to the external electrode. The member paste was applied and dried. Further, the connection member paste was applied and dried so as to cover only the exposed surface of the protruding portion of the first internal electrode layer connected to the external electrode.
[0046]
Next, a binder removal treatment was performed under the following conditions, and then fired to form external electrodes and connection members.
(Binder removal conditions)
Temperature increase rate: 30 ° C / hour
Holding temperature: 300 ° C
Temperature holding time: 5 hours
Atmosphere: In the air
(Baking conditions)
Holding temperature: 950 ° C
Temperature holding time: 10 minutes
Atmosphere: N₂+ H₂atmosphere
[0047]
Next, the resistor paste is formed by coating and drying the resistor paste so as to cover the two connecting members formed as described above and to be separated from the external electrodes, and then firing under the following conditions. A composite electronic component was produced.
(Baking conditions)
Holding temperature: 850 ° C
Temperature holding time: 10 minutes
Atmosphere: In the air
[0048]
【The invention's effect】
As described above in detail, according to the present invention, the resistor is located at a position connecting the first internal electrode layer connected to the external electrode and the other first internal electrode layer, and is separated from the external electrode. Because it is in a state, it is hardly affected by the heat at the time of soldering the external electrode, the deterioration of the resistor due to heat is prevented, and it is difficult to cause a short circuit between the external electrode and the resistor at the time of soldering the external electrode. A resistance value is obtained. Furthermore, it is not necessary to incorporate a resistor in the laminated body, the manufacturing is easy, and the resistance value can be easily adjusted by selecting various resistors to be used.
[Brief description of the drawings]
FIG. 1 is a perspective view showing an embodiment of a composite electronic component of the present invention.
2 is a cross-sectional view taken along line AA of the composite potential component shown in FIG.
3 is a perspective view showing a state in which an external electrode and a resistor are removed from the composite electronic component shown in FIG. 1. FIG.
4 is a perspective view showing a state in which only the first internal electrode layer and the second internal electrode layer are extracted from the composite electronic component shown in FIG. 1; FIG.
FIG. 5 is a cross-sectional view corresponding to FIG. 2 showing another embodiment of the composite electronic component of the present invention.
6 is a perspective view corresponding to FIG. 3, showing a state where external electrodes and resistors are removed from the composite electronic component shown in FIG. 5;
7 is a perspective view corresponding to FIG. 4 showing a state in which only the first internal electrode layer and the second internal electrode layer are extracted from the composite electronic component shown in FIG. 5;
FIG. 8 is a perspective view showing a first internal electrode layer and a second internal electrode layer in another embodiment of the composite electronic component of the present invention.
[Explanation of symbols]
1,11 ... Composite electronic parts
2,12 ... Laminated body
3, 4, 13, 14 ... external electrode
5,15 ... resistor
6, 16 ... first internal electrode layer
16 '... outer internal electrode layer
16 "... inner internal electrode layer
6a, 6b, 16'a, 16 "a, 16b ... protrusion
7, 17 ... second internal electrode layer
8a, 8b, 18a, 18b ... connecting member
9, 19 ... Dielectric layer

Claims (1)

In a composite electronic component comprising a laminate in which a plurality of internal electrode layers are laminated via a dielectric layer, and a pair of external electrodes provided on opposite end surfaces of the laminate,
The internal electrode layer includes a first internal electrode layer and a second internal electrode layer alternately stacked via dielectric layers, and a layer excluding at least one of the plurality of first internal electrode layers is the stacked body. Are connected to one external electrode, and at least one of the first internal electrode layers connected to the external electrode has an electrically insulated outer internal electrode layer and inner internal electrode Divided into layers, only the outer internal electrode layer is drawn to one end face of the laminate and connected to the external electrode, and the area of the outer internal electrode layer is smaller than the area of the inner internal electrode layer A plurality of the second internal electrode layers are drawn out to the other end face of the laminate and connected to the other external electrode,
Each first internal electrode layer including the outer internal electrode layer and the inner internal electrode layer has a protruding portion exposed on a side surface of the multilayer body, and of the protruding portions, the exposed portion of the inner internal electrode layer is exposed. The exposed surface of the protruding portion of the first internal electrode layer that is not connected to the surface and the external electrode is connected by a connection member disposed on the side surface,
A resistor is disposed on the side surface so as to connect the protruding portion of the outer internal electrode layer connected to the external electrode and the connecting member, and the resistor is in contact with the pair of external electrodes. complex electronic device wherein there.

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