JP5254260B2 - Printing method of conductive electrode - Google Patents

Description

  The present invention relates to a method for printing a conductive electrode in a through-hole provided in a substrate, and more particularly, to a method for printing a conductive electrode in a through-hole provided in a ceramic green sheet serving as a ceramic layer of a multilayer sensor element. .

Conventionally, various measuring devices have been used to know the concentration of a desired gas component in a gas to be measured. For example, a gas sensor having a sensor element in which a plurality of solid electrolyte layers having oxygen ion conductivity such as zirconia (ZrO ₂ ) are stacked is known as an apparatus for measuring NOx concentration in a measurement gas such as combustion gas. is there.

  In such a gas sensor, the conduction between the conductive parts formed on the front and back surfaces of the solid electrolyte layer is improved by forming a conductive electrode in a through hole provided penetrating in the thickness direction of the solid electrolyte. (See Patent Document 1). In addition, there is a gas sensor in which the insulation property of the solid electrolyte is maintained by forming a conductive electrode in a through hole having an insulating layer coated on the inner wall (see Patent Document 2).

JP-A-8-271476 JP 2001-242129 A

  The formation of the conductive electrode in the gas sensor as disclosed in Patent Documents 1 and 2 is performed by, for example, metal mask printing. Specifically, first, a print mask provided with a through hole having substantially the same opening diameter as the through hole is placed on a green sheet provided with the through hole, and the conductive material supplied on the print mask is arranged. By moving the paste with a squeegee, the through-hole is filled with the conductive paste. Then, the filled conductive paste is dried, and the green sheet is pressed from above and below, whereby a conductive electrode is formed in the through hole. More precisely, a conductive electrode is formed by the subsequent evaporating of the organic component in the conductive paste and the sintering of the conductive metal by a firing process, but in this specification, for convenience of explanation, The conductive paste present in the through hole after pressing may be referred to as a conductive electrode.

  In the case of metal mask printing, the shape of the conductive electrode to be formed is mainly determined according to the viscosity of the conductive paste, the opening diameter and depth of the through hole, the moving speed of the squeegee, and the angle of the squeegee. Therefore, in order to print the conductive electrodes in a good shape in the through holes, it is necessary to accurately control them.

  However, it is difficult to accurately control the viscosity of the conductive paste. When the viscosity of the conductive paste deviates from a predetermined range, the conductive electrode sinks or protrudes from the surface of the solid electrolyte, resulting in poor appearance or electrical conductivity. There was a problem of causing defects.

  Specifically, if the viscosity of the conductive paste is lower than a predetermined range, the drying shrinkage rate of the conductive paste increases and the amount of the conductive paste filled in the through hole decreases. It is formed in a shape that is recessed from the surface of the green sheet in the hole. When the conductive electrode has such a shape, there are problems such as deterioration in yield due to poor appearance and poor conduction between the conductive parts formed on the front and back surfaces of the solid electrolyte.

  On the other hand, when the viscosity of the conductive paste is higher than the predetermined range, the tip of the conductive paste remains protruding and remaining above the surface of the green sheet even after drying shrinkage. If the pressing process is performed with the conductive paste in such a shape, the protruding part may be peeled off and attached to other parts, or the tip of the conductive electrode may be formed in a shape protruding from the surface of the green sheet. There are things to do. When such adhesion occurs, there are problems such as deterioration in yield due to poor appearance and poor connection such as short circuit between terminals. In addition, when the tip of the conductive electrode is formed so as to protrude from the surface of the green sheet, when the connector pattern is printed on the green sheet so as to include the conductive electrode in a later step, the connector pattern is curved and the curved There was also a problem that an appearance defect was caused due to.

  The present invention has been made in view of the above problems, and an object thereof is to provide a printing method capable of printing a conductive electrode having a good shape in a through hole of a substrate.

The invention of claim 1 is a method of printing a conductive electrode in a through hole provided in a green sheet and having an opening diameter of 300 μm to 900 μm and a depth of 100 μm to 800 μm , comprising: (a) on a table (B) a metal mask having a thickness of 40 μm to 60 μm and having a through hole, aligning the through hole and the through hole , and forming a gap on the green sheet and fixing spaced, the first squeegee (c) hardness of 60 ° or less, the metal mask while maintaining the contact angle with respect to the metal mask 15 ° to 45 ° to the pressing article al before Symbol metal mask by moving the following moving speed 30 mm / sec along, 4000Pa · s~8000Pa · s der supplied viscosity at room temperature over the metallic mask A conductive paste to fill in the through hole, depositing said through hole in said conductive paste to above the top, (d) a second squeegee, 30 ° contact angle with respect to the metal mask 75 by the pressing Shinano said metal mask at a constant temperature of ° be moved in 50 mm / sec or less of the traveling speed along the et before Symbol metal mask, the conductive paste deposited on the through hole one A step of scraping a part, (e) a step of drying the conductive paste, and (f) a step of pressing the green sheet from above and below. In the step (d), the step (e ) And after the step (f), the conductive paste is scraped off so that the conductive paste is filled into the through hole without excess or deficiency. .

  Invention of Claim 2 is the printing method of the conductive electrode of Claim 1, Comprising: After the said process (f), a connector pattern is printed so that the said through hole may be included on the said green sheet And in the step (a), the green sheet is fixed on the table so that the longitudinal direction of the connector pattern coincides with the direction in which the first squeegee moves. .

  A third aspect of the invention is the conductive electrode printing method according to the second aspect, wherein the step (g) prints the same connector pattern twice.

A fourth aspect of the present invention, a printing method conductive electrode according to any of claims 1 to 3, wherein step (a), at least the through hole is provided of the rear surface of the front Symbol greensheet The green sheet is fixed to the table after a PET tape is laid so as to include the formed region.

According to the first to fourth aspects of the invention, it is possible to realize a conductive electrode printed in a good shape inside the through hole of the substrate.

  According to the second aspect of the present invention, by causing the bleeding that has occurred outside the through hole to be a part of the connector pattern, it is possible to prevent the appearance failure and the conduction failure caused by the bleeding.

It is the cross-sectional schematic diagram which showed schematically an example of the structure of the gas sensor. It is a disassembled perspective view of a sensor element. It is a figure which shows the flow of a process at the time of producing | generating a sensor element. It is a cross-sectional schematic diagram which shows an example of a structure of an embedding printing apparatus roughly. It is a figure which shows the flow of a process at the time of printing a conduction electrode in a through hole using the printing method which concerns on this Embodiment. It is the cross-sectional schematic diagram which showed the process in which a conduction electrode is printed in a through hole using the printing method which concerns on this Embodiment. It is the cross-sectional schematic diagram which showed the mode of the electrically conductive paste in the formation process of a conduction electrode. It is the cross-sectional schematic diagram which showed a mode that the conduction electrode was printed in the through hole using the printing method which concerns on this Embodiment. It is the figure which showed the mode of the upper surface of the green sheet after performing a press process and the conduction electrode was formed. It is a schematic diagram which shows the mode of formation of a bleed. It is the figure which showed the mode of the upper surface of the green sheet after the 1st connector pattern was printed. It is the figure which showed the mode of the upper surface of the green sheet after the 2nd connector pattern was printed. It is a figure which shows the result of having performed the external appearance test | inspection and the warpage test | inspection of the connector pattern about the green sheet in which the conductive electrode was printed using the printing method which concerns on this Embodiment, and the green sheet which concerns on a comparative example.

<Schematic configuration of gas sensor>
First, a schematic configuration of the gas sensor 100 including a conductive electrode printed using the printing method of the present invention will be described.

FIG. 1 is a schematic cross-sectional view schematically showing an example of the configuration of the gas sensor 100. The sensor element 101 includes a first substrate layer 1, a second substrate layer 2, a third substrate layer 3, and a first solid electrolyte layer 4 each made of an oxygen ion conductive solid electrolyte layer such as zirconia (ZrO ₂ ). The spacer layer 5 and the second solid electrolyte layer 6 are elongated and long plate-like elements having a structure in which they are laminated in this order from the bottom in the drawing. The solid electrolyte forming these six layers is dense and airtight. The sensor element 101 is manufactured, for example, by performing predetermined processing and circuit pattern printing on a ceramic green sheet corresponding to each layer, stacking them, and firing and integrating them.

  One end of the sensor element 101, and between the lower surface of the second solid electrolyte layer 6 and the upper surface of the first solid electrolyte layer 4, is a gas inlet 10, a first diffusion rate limiting unit 11, and a buffer space. 12, the second diffusion rate limiting part 13, the first internal space 20, the third diffusion rate limiting part 30, and the second internal space 40 are adjacently formed in such a manner that they communicate in this order.

  The gas introduction port 10, the buffer space 12, the first internal space 20, and the second internal space 40 are provided on the lower surface of the second solid electrolyte layer 6 with the upper portion provided in a state in which the spacer layer 5 is cut out. The space inside the sensor element 101 is defined by the lower part being the upper surface of the first solid electrolyte layer 4 and the side parts being the side surfaces of the spacer layer 5.

  Each of the first diffusion rate controlling unit 11, the second diffusion rate controlling unit 13, and the third diffusion rate controlling unit 30 is provided as two horizontally long slits (the opening has a longitudinal direction in a direction perpendicular to the drawing). . In addition, the site | part from the gas inlet 10 to the 2nd internal space 40 is also called a gas distribution part.

  Further, at a position farther from the front end side than the gas circulation part, the side part is partitioned by the side surface of the first solid electrolyte layer 4 between the upper surface of the third substrate layer 3 and the lower surface of the spacer layer 5. The reference gas introduction space 43 is provided at the position. For example, the atmosphere is introduced into the reference gas introduction space 43 as a reference gas when measuring the NOx concentration.

  The atmosphere introduction layer 48 is a layer made of porous alumina, and the reference gas is introduced into the atmosphere introduction layer 48 through the reference gas introduction space 43. The air introduction layer 48 is formed so as to cover the reference electrode 42.

  The reference electrode 42 is an electrode formed in such a manner that it is sandwiched between the upper surface of the third substrate layer 3 and the first solid electrolyte layer 4. As described above, the reference electrode 42 leads to the reference gas introduction space 43. An air introduction layer 48 is provided. Further, as will be described later, it is possible to measure the oxygen concentration (oxygen partial pressure) in the first internal space 20 and the second internal space 40 using the reference electrode 42.

  In the gas circulation part, the gas inlet 10 is a part opened to the external space, and the gas to be measured is taken into the sensor element 101 from the external space through the gas inlet 10.

  The first diffusion control unit 11 is a part that provides a predetermined diffusion resistance to the gas to be measured taken from the gas inlet 10.

  The buffer space 12 is a space provided to guide the gas to be measured introduced from the first diffusion rate controlling unit 11 to the second diffusion rate controlling unit 13.

  The second diffusion rate limiting unit 13 is a part that imparts a predetermined diffusion resistance to the gas to be measured introduced from the buffer space 12 into the first internal space 20.

  When the gas to be measured is introduced from the outside of the sensor element 101 to the inside of the first internal space 20, the pressure fluctuation of the gas to be measured in the external space (exhaust pressure pulsation if the gas to be measured is an automobile exhaust gas) ), The gas to be measured that is suddenly taken into the sensor element 101 from the gas inlet 10 is not directly introduced into the first internal space 20, but the first diffusion control unit 11, the buffer space 12, the second After the concentration variation of the gas to be measured is canceled through the diffusion control unit 13, the gas is introduced into the first internal space 20. As a result, the concentration fluctuation of the gas to be measured introduced into the first internal space is almost negligible.

  The first internal space 20 is provided as a space for adjusting the partial pressure of oxygen in the gas to be measured introduced through the second diffusion rate limiting unit 13. The oxygen partial pressure is adjusted by the operation of the main pump cell 21.

  The main pump cell 21 includes an inner pump electrode 22 having a ceiling electrode portion 22a provided on substantially the entire lower surface of the second solid electrolyte layer 6 facing the first internal space 20, and an upper surface of the second solid electrolyte layer 6. An electrochemical pump cell comprising an outer pump electrode 23 provided in a manner exposed to the external space in a region corresponding to the ceiling electrode portion 22a, and a second solid electrolyte layer 6 sandwiched between these electrodes. is there.

  The inner pump electrode 22 is formed across the upper and lower solid electrolyte layers (the second solid electrolyte layer 6 and the first solid electrolyte layer 4) that define the first inner space 20, and the spacer layer 5 that provides side walls. Yes. Specifically, a ceiling electrode portion 22a is formed on the lower surface of the second solid electrolyte layer 6 that provides the ceiling surface of the first internal space 20, and a bottom portion is formed on the upper surface of the first solid electrolyte layer 4 that provides the bottom surface. Spacer layers in which the electrode portions 22b are formed and the side electrode portions (not shown) constitute both side walls of the first internal space 20 so as to connect the ceiling electrode portions 22a and the bottom electrode portions 22b. 5 is formed on the side wall surface (inner surface), and is disposed in a tunnel-shaped structure at the portion where the side electrode portion is disposed.

The inner pump electrode 22 and the outer pump electrode 23 are formed as a porous cermet electrode (for example, a cermet electrode of Pt and ZrO ₂ containing 1% of Au). The inner pump electrode 22 in contact with the gas to be measured is formed using a material that has a reduced or no reducing ability for the NOx component in the measured gas.

  In the main pump cell 21, a desired pump voltage Vp 0 is applied between the inner pump electrode 22 and the outer pump electrode 23, and the pump current is positive or negative between the inner pump electrode 22 and the outer pump electrode 23. By flowing Ip0, oxygen in the first internal space 20 can be pumped into the external space, or oxygen in the external space can be pumped into the first internal space 20.

  In order to detect the oxygen concentration (oxygen partial pressure) in the atmosphere in the first internal space 20, the inner pump electrode 22, the second solid electrolyte 6, the spacer layer 5, the first solid electrolyte 4, The third substrate layer 3 and the reference electrode 42 constitute an electrochemical sensor cell, that is, an oxygen partial pressure detection sensor cell 80 for main pump control.

  By measuring the electromotive force V0 in the main pump control oxygen partial pressure detection sensor cell 80, the oxygen concentration (oxygen partial pressure) in the first internal space 20 can be known. Further, the pump current Ip0 is controlled by feedback control of Vp0 so that the electromotive force V0 is constant. Thereby, the oxygen concentration in the first internal space 20 can be kept at a predetermined constant value.

  The third diffusion control unit 30 provides a predetermined diffusion resistance to the gas under measurement whose oxygen concentration (oxygen partial pressure) is controlled by the operation of the main pump cell 21 in the first internal space 20, and the gas under measurement is supplied to the gas under measurement. This is the part that leads to the second internal space 40.

  The second internal space 40 is provided as a space for performing a process related to the measurement of the nitrogen oxide (NOx) concentration in the gas to be measured introduced through the third diffusion control unit 30. The NOx concentration is measured mainly in the second internal space 40 in which the oxygen concentration is adjusted by the auxiliary pump cell 50, and further by measuring the pump cell 41 for measurement.

  In the second internal space 40, after the oxygen concentration (oxygen partial pressure) is adjusted in the first internal space 20 in advance, the auxiliary pump cell 50 further supplies the gas to be measured introduced through the third diffusion control unit. The oxygen partial pressure is adjusted. Thereby, since the oxygen concentration in the second internal space 40 can be kept constant with high accuracy, the gas sensor 100 can measure the NOx concentration with high accuracy.

  The auxiliary pump cell 50 includes an auxiliary pump electrode 51 having a ceiling electrode portion 51a provided on substantially the entire lower surface of the second solid electrolyte layer 6 facing the second internal space 40, and an outer pump electrode 23 (outer pump electrode 23). The auxiliary electrochemical pump cell is configured by the second solid electrolyte layer 6 and the sensor element 101 and an appropriate electrode on the outside.

  The auxiliary pump electrode 51 is disposed in the second internal space 40 in the same tunnel configuration as the inner pump electrode 22 provided in the first internal space 20. That is, the ceiling electrode portion 51 a is formed on the second solid electrolyte layer 6 that provides the ceiling surface of the second internal space 40, and the first solid electrolyte layer 4 that provides the bottom surface of the second internal space 40 is formed on the first solid electrolyte layer 4. The bottom electrode part 51b is formed, and the side electrode part (not shown) connecting the ceiling electrode part 51a and the bottom electrode part 51b is provided on the spacer layer 5 that provides the side wall of the second internal space 40. It has a tunnel-type structure formed on both wall surfaces.

  Note that the auxiliary pump electrode 51 is also formed using a material having a reduced reduction ability or no reduction ability with respect to the NOx component in the gas to be measured, like the inner pump electrode 22.

  In the auxiliary pump cell 50, by applying a desired voltage Vp1 between the auxiliary pump electrode 51 and the outer pump electrode 23, oxygen in the atmosphere in the second internal space 40 is pumped to the external space, or It is possible to pump into the second internal space 40 from the space.

  Further, in order to control the oxygen partial pressure in the atmosphere in the second internal space 40, the auxiliary pump electrode 51, the reference electrode 42, the second solid electrolyte layer 6, the spacer layer 5, and the first solid electrolyte. The layer 4 and the third substrate layer 3 constitute an electrochemical sensor cell, that is, an auxiliary pump control oxygen partial pressure detection sensor cell 81.

  The auxiliary pump cell 50 performs pumping by the variable power source 52 that is voltage-controlled based on the electromotive force V1 detected by the auxiliary pump control oxygen partial pressure detection sensor cell 81. Thereby, the oxygen partial pressure in the atmosphere in the second internal space 40 is controlled to a low partial pressure that does not substantially affect the measurement of NOx.

  At the same time, the pump current Ip1 is used to control the electromotive force of the oxygen partial pressure detection sensor cell 80 for main pump control. Specifically, the pump current Ip1 is input as a control signal to the main pump control oxygen partial pressure detection sensor cell 80, and the electromotive force V0 is controlled, so that the third diffusion rate limiting unit 30 controls the second internal space. The gradient of the oxygen partial pressure in the gas to be measured introduced into the gas 40 is controlled so as to be always constant. When used as a NOx sensor, the oxygen concentration in the second internal space 40 is maintained at a constant value of about 0.001 ppm by the action of the main pump cell 21 and the auxiliary pump cell 50.

  The measurement pump cell 41 measures the NOx concentration in the gas to be measured in the second internal space 40. The measurement pump cell 41 includes a measurement electrode 44 provided on a top surface of the first solid electrolyte layer 4 facing the second internal space 40 and spaced from the third diffusion rate-determining portion 30, an outer pump electrode 23, The electrochemical pump cell is constituted by the second solid electrolyte layer 6, the spacer layer 5, and the first solid electrolyte layer 4.

  The measurement electrode 44 is a porous cermet electrode. The measurement electrode 44 also functions as a NOx reduction catalyst that reduces NOx present in the atmosphere in the second internal space 40. Further, the measurement electrode 44 is covered with a fourth diffusion rate controlling part 45.

The fourth diffusion rate-determining part 45 is a film composed of a porous body mainly composed of alumina (Al ₂ O ₃ ). The fourth diffusion control unit 45 plays a role of limiting the amount of NOx flowing into the measurement electrode 44 and also functions as a protective film for the measurement electrode 44.

  In the measurement pump cell 41, oxygen generated by the decomposition of nitrogen oxides in the atmosphere around the measurement electrode 44 can be pumped out, and the generated amount can be detected as the pump current Ip2.

  In order to detect the partial pressure of oxygen around the measurement electrode 44, the second solid electrolyte layer 6, the spacer layer 5, the first solid electrolyte layer 4, the third substrate layer 3, the measurement electrode 44, The reference electrode 42 constitutes an electrochemical sensor cell, that is, a measurement pump control oxygen partial pressure detection sensor cell 82. The variable power supply 46 is controlled on the basis of the electromotive force V2 detected by the measurement pump control oxygen partial pressure detection sensor cell 82.

The gas to be measured introduced into the second internal space 40 reaches the measurement electrode 44 through the fourth diffusion rate-determining unit 45 under the condition where the oxygen partial pressure is controlled. Nitrogen oxide in the gas to be measured around the measurement electrode 44 is reduced (2NO → N ₂ + O ₂ ) to generate oxygen. The generated oxygen is pumped by the measurement pump cell 41. At this time, the variable power source is set so that the control voltage V2 detected by the measurement pump control oxygen partial pressure detection sensor cell 82 becomes constant. The voltage Vp2 is controlled. Since the amount of oxygen generated around the measurement electrode 44 is proportional to the concentration of nitrogen oxide in the gas to be measured, the nitrogen oxide in the gas to be measured using the pump current Ip2 in the measurement pump cell 41. The concentration will be calculated.

  The second solid electrolyte layer 6, the spacer layer 5, the first solid electrolyte layer 4, the third substrate layer 3, the outer pump electrode 23, and the reference electrode 42 constitute an electrochemical sensor cell 83. The oxygen partial pressure in the gas to be measured outside the sensor can be detected by the electromotive force Vref obtained by the sensor cell 83.

  In the gas sensor 100 having such a configuration, by operating the main pump cell 21 and the auxiliary pump cell 50, the oxygen partial pressure is always kept at a constant low value (a value that does not substantially affect the measurement of NOx). A gas to be measured is supplied to the measurement pump cell 41. Therefore, the NOx concentration in the measurement gas is determined based on the pump current Ip2 that flows when oxygen generated by the reduction of NOx is pumped out of the measurement pump cell 41 in proportion to the NOx concentration in the measurement gas. You can know.

  Furthermore, the sensor element 101 includes a heater unit 70 that plays a role of temperature adjustment for heating and maintaining the sensor element 101 in order to increase the oxygen ion conductivity of the solid electrolyte. The heater unit 70 includes a heater electrode 71, a heater 72, a through hole 73, a heater insulating layer 74, a pressure dissipation hole 75, and a conduction electrode 76.

  The heater electrode 71 is an electrode formed so as to be in contact with the lower surface of the first substrate layer 1. By connecting the heater electrode 71 to an external power source, power can be supplied to the heater unit 70 from the outside.

  The heater 72 is an electric resistor formed in a form sandwiched between the second substrate layer 2 and the third substrate layer 3 from above and below. The heater 72 generates heat by being supplied with power from outside, and heats and keeps the solid electrolyte forming the sensor element 101.

  The heater 72 is embedded over the entire area from the first internal space 20 to the second internal space 40, and the entire sensor element 101 can be adjusted to a temperature at which the solid electrolyte is activated. ing.

  The through hole 73 is a through hole provided in the thickness direction of the first substrate layer 1 and the second substrate layer 2, and has a conductive electrode 76 provided therein.

  The heater insulating layer 74 is an insulating layer formed on the upper and lower surfaces of the heater 72 by an insulator such as alumina. The heater insulating layer 74 is formed for the purpose of obtaining electrical insulation between the second substrate layer 2 and the heater 72 and electrical insulation between the third substrate layer 3 and the heater 72.

  The pressure dissipating hole 75 is a portion that is provided so as to penetrate the third substrate layer 3 and communicate with the reference gas introduction space 43, and is for the purpose of alleviating the increase in internal pressure accompanying the temperature increase in the heater insulating layer 74. Formed.

  The conductive electrode 76 is a conductor provided in the through hole 73 and electrically connects the heater electrode 71 and the heater 72. The conductive electrode 76 is made of, for example, a noble metal such as platinum or a refractory metal such as tungsten or molybdenum.

<Detailed configuration of heater section>
FIG. 2 is an exploded perspective view of the sensor element 101 for more specifically explaining the configuration of the heater unit 70. In FIG. 2, for simplification of illustration, the first substrate layer 1 and the second substrate layer 2 are simplified as one rectangular parallelepiped. Similarly, the third substrate layer 3, the first solid electrolyte layer 4, the spacer layer 5, and the second solid electrolyte layer 6 are simplified as one rectangular parallelepiped. Further, the heater insulating layer 74 is omitted.

  A first heater electrode 71 a and a second heater electrode 71 b are formed as the heater electrode 71 on the lower surface of the first substrate layer 1. The first heater electrode 71a and the second heater electrode b are connected to the heater 72 by a conductive electrode 76 provided in the through hole 73, respectively. By connecting an external power source between the first heater electrode 71a and the second heater electrode 71b and applying a voltage between the electrodes, the heater 72 generates heat.

  Specifically, the first heater end 72a, which is one end of the heater 72, is electrically connected to the first heater electrode 71a via the first conduction electrode 76a in the first through hole 73a. . Similarly, the second heater end 72b, which is the other end, is electrically connected to the second heater electrode 71b via the second conduction electrode 76b in the second through hole 73b.

<Manufacturing process of sensor element>
Next, a process for manufacturing the sensor element 101 described above will be described.

  FIG. 3 is a diagram showing a flow of processing when the sensor element 101 is created. When producing the sensor element 101, first, a green sheet containing an oxygen ion conductive solid electrolyte such as zirconia as a ceramic component is prepared (step 1). In the case of creating the sensor element 101 according to the present embodiment, six green sheets are prepared corresponding to each layer.

  Next, with respect to the green sheet corresponding to the layers constituting the internal space and the through hole 73, a penetrating portion corresponding to the internal space and the through hole 73 is formed by a punching process using a punching device (step 2).

  When the green sheet corresponding to each layer is prepared, the conductive electrode 76 is printed and dried on the green sheet in which the through hole 73 is formed (step 3). In the present embodiment, the method of printing the conductive electrode 76 in the through hole 73 is characteristic for realizing a good gas sensor, and details thereof will be described later. A known drying means can be used for the drying process after printing.

  When the conductive electrode is formed, pattern printing / drying processing is performed on each green sheet (step 4). A known screen printing technique can be used for pattern printing. Also, a known drying means can be used for the drying process after printing.

  When the pattern printing is finished, printing / drying processing of an adhesive paste for laminating and bonding the green sheets corresponding to the respective layers is performed (step 5). Also for the printing process and drying process at this time, known printing means and drying means can be used.

  Subsequently, the green sheets to which the adhesive has been applied are stacked in a predetermined order, and are subjected to pressure bonding by applying predetermined temperature and pressure conditions to perform a pressure bonding process to form a single laminate (step 6). Specifically, it is performed by heating and pressurizing the entire stacking jig with a laminating machine such as a known hydraulic press machine. The pressure, temperature, and time for performing heating and pressurization depend on the laminating machine to be used, but appropriate conditions may be determined so that good lamination can be realized.

  When a laminated body is obtained as described above, subsequently, a plurality of portions of the laminated body are cut by a known cutting device and cut into individual units of the sensor element 101 (step 7). Then, the sensor element 101 as described above is generated by firing the cut-out element body under predetermined conditions (step 8).

<Embedded printing device>
Hereinafter, a mode in which the conductive electrode 76 is printed in the through hole 73 will be specifically described. First, an embedded printing apparatus as an example of an apparatus used for printing the conductive electrode 76 in the through hole 73 will be described. FIG. 4 is a schematic cross-sectional view schematically illustrating an example of the configuration of the embedded printing apparatus 200. As shown in FIG. 4, the embedded printing apparatus 200 mainly includes a table 201, a fixing member 202, a first squeegee unit 203, a second squeegee unit 204, a driving unit 205, and a control unit 206. 4, an xy coordinate in which a direction in which a first squeegee unit 203 described later moves on the green sheet 300 is an x-axis direction, and a direction perpendicular to the upper surface of the arranged green sheet 300 is a y-axis direction. (The same applies to the following).

  The table 201 is a part for mounting and fixing the green sheet 300 on the upper surface thereof. The fixing member 202 is a member that fixes the metal mask 310 provided with the through hole 311 having substantially the same opening diameter as the through hole 73. 4 shows a state in which the green sheet 300 is placed and fixed on the table 201, the metal mask 310 is held and fixed by the fixing member 202, and the conductive paste 320 is supplied onto the metal mask 310. Yes. The fixing means 202 fixes the metal mask 310 so as to be located immediately above the through hole 73. Preferably, the table 201 is provided with a large number of suction holes (not shown), and the green sheet 300 is sucked and fixed onto the table 201 by applying a negative pressure to the suction holes by suction means (not shown). Is done.

  The first squeegee unit 203 is formed in a flat shape, a square shape, a sword shape, or the like, and includes a first squeegee 203a made of a material such as rubber mainly composed of urethane, and first holding means 203b that holds the first squeegee 203a. With. The first squeegee 203a is a member that scrapes off the conductive paste 320 supplied onto the metal mask 310 in the positive x-axis direction. The second squeegee unit 204 is formed in a flat shape, a square shape, a sword shape, or the like, and a second squeegee 204a made of a material such as rubber mainly composed of urethane, and a second holding for holding the second squeegee 204a. Means 204b. The second squeegee 204a is a member that scrapes off the conductive paste 320 supplied on the metal mask 310 in the negative x-axis direction.

  In the embedded printing apparatus 200, as shown in FIG. 4, in a state where the green sheet 300 and the metal mask 310 are arranged and the conductive paste 32 is supplied, the control unit 206 is operated by the first squeegee unit 203 by the driving unit 205. By appropriately controlling the operation of each part including the driving operation of the second squeegee unit 204, the conductive paste 320 is filled into the through hole 73 of the green sheet 300 (that is, the conductive electrode 76 is printed). .

  Specifically, the first squeegee 203a moves on the metal mask 310 in the x-axis positive direction while pressing the metal mask 310 in the y-axis negative direction, so that the conductivity supplied on the metal mask 310 is obtained. Then, the second squeegee 204a is moved in the negative x-axis direction over the metal mask 310 while pressing the metal mask 310 in the negative y-axis direction. By scraping off a part of the conductive paste 320 deposited above the through-hole 73, a series of printing processes are performed.

  However, when the metal mask 310 receives the force from the first squeegee 203a and the second squeegee 204a during printing and the metal mask 310 is bent in the negative y-axis direction, the metal mask 310 and the vicinity of the through-hole 311 of the metal mask 310 are green. The sheet 300 is fixed with an interval of contact with the vicinity of the through hole 73 of the sheet 300. This is to prevent the green sheet 300 from being damaged by receiving a force from the metal mask 310 due to contact with the metal mask 310.

  As the metal mask 310, the first squeegee 203a, and the second squeegee 204a, appropriate ones according to the printing purpose can be used. In the present embodiment, the thickness of the metal mask 310 is set to 40 μm to 60 μm, and the first One squeegee 203a having a contact angle of 15 ° to 45 ° and a hardness of 60 ° or less is used, and the second squeegee 204a having a contact angle of 30 ° to 75 ° is used. These form a conductive electrode 76 having a good shape that fills the through-hole 73 without gaps and does not protrude from the surface of the green sheet 300 when performing metal mask printing using a conductive paste under the conditions described later. It is a condition that makes possible. The contact angle refers to the lower surface (203c and the second squeegee 204a in the moving direction of the first squeegee 203a and the second squeegee 204a with respect to the surface of the metal mask 310 when the first squeegee 203a and the second squeegee 204a are in contact with the metal mask 310. 204c).

<Printing method of conductive electrode>
Next, a method for printing the conductive electrode 76 in the through hole 73 will be described. FIG. 5 is a diagram showing a flow of processing when the conductive electrode 76 is printed in the through hole 73. FIG. 6 is a schematic cross-sectional view illustrating a process in which the conductive electrode 76 is printed in the through hole 73 using the conductive electrode printing method according to the present embodiment. In FIG. 6, illustration of the drive means 205 and the control means 206 is abbreviate | omitted for simplification of description. FIG. 7 is a schematic cross-sectional view showing the state of the conductive paste 320 in the process of forming the conductive electrode 76. FIG. 8 is a schematic cross-sectional view showing a state in which the conductive electrode 76 is printed in the through hole 73 using the conductive electrode printing method according to the present embodiment. In the present embodiment, a case where the conductive electrode 76 is printed in the through hole 73 of the general gas sensor 100 having an opening diameter of 300 μm to 900 μm and a depth of 100 μm to 800 μm will be described as an example.

  First, the green sheet 300 in which the through hole 73 is formed is placed and fixed on the table 201 of the embedded printing apparatus 200 (step 11). At this time, the green sheet 300 is placed and fixed so that the longitudinal direction (see FIG. 10) of the connector pattern printed in the subsequent process matches the x-axis direction. As described later, such a green sheet 300 mounting mode is employed in order to positively use the bleeding portion of the conductive paste 320 formed on the surface of the green sheet 300 as a part of the connector pattern. It has been done.

  Preferably, when the green sheet 300 is placed on the table 201, for example, a PET film or the like is laid on the back surface of the green sheet 300 below at least a portion where the through hole 73 is provided. By laying such a PET film, the conductive paste 320 is prevented from leaking between the through hole 73 and the table 201 when the conductive paste 320 is filled in the through hole 73 in a later process. The

  When the green sheet 300 is fixed, the metal mask 310 is aligned so that the through hole 311 is positioned above the through hole 73, and the gap between the green sheet 300 (in this embodiment, about 0.2 mm). And the metal mask 310 is fixed to the fixing means 202 (step 12).

  Subsequently, the conductive paste 320 is supplied onto the metal mask 310 by a supply means (not shown), for example (step 13).

  As the conductive paste 320, for example, a paste made of a noble metal such as platinum or a refractory metal such as tungsten or molybdenum is used. The conductive paste is adjusted so that the viscosity at normal temperature is 4000 Pa · s to 8000 Pa · s.

  Subsequently, the first squeegee unit 203 is moved in the y-axis negative direction by the driving means 205, and the metal mask 310 is moved so that the vicinity of the through hole 73 of the green sheet 300 and the vicinity of the through hole 311 of the metal mask 310 are in contact with each other. The first squeegee unit 203 is moved in the positive x-axis direction while being pressed by the first squeegee 203a (step 14).

  The moving speed of the first squeegee unit 203 in the positive x-axis direction is set to 30 mm / sec or less.

  As a result, the conductive paste 320 is filled in the through hole 73 and is also deposited in a protruding shape above the through hole 73 (FIGS. 6A and 7A). This is because the conductive paste 320 has a relatively high viscosity of 4000 Pa · s to 8000 Pa · s as described above.

  When the movement of the first squeegee unit 203 in the positive x-axis direction is completed, the driving means 205 moves the second squeegee unit 204 in the negative y-axis direction, and the contact state between the green sheet 300 and the metal mask 310 is maintained. As described above, the first squeegee unit 203 is moved in the positive y-axis direction while the metal mask 310 is pressed in the negative y-axis direction by the second squeegee unit 204 so that the first squeegee 203a and the metal mask 310 are not in contact with each other. (Step 15, FIG. 6B). Subsequently, the second squeegee unit 204 is moved in the x-axis negative direction while the metal mask 310 is pressed by the driving means 205 (step 16).

  The moving speed of the second squeegee unit 204 in the negative x-axis direction is set to 50 mm / sec or less.

  As a result, a part 321 of the protruding portion of the conductive paste 320 from the through hole 73 is scraped off by the second squeegee 204 a, but the protruding portion 322 of the conductive paste 320 exists above the through hole 73. (FIG. 6 (c), FIG. 7 (b)).

  When the movement of the second squeegee unit 204 in the negative x-axis direction is completed, the green sheet 300 is taken out from the embedding printing apparatus 200, the conductive paste 320 is cured by a known drying means, and then the PET film is peeled off (step 17). . Then, the conductive paste shrinks by drying, and the protruding portion 322 of the conductive paste 320 above the through hole 73 shrinks before drying (FIG. 7C).

  Subsequently, the green sheet 300 is evenly pressed from above and below with a known laminating press (step 18). The protruding portion 322 of the conductive paste 320 is pushed into the through hole 73 by the pressing, and a state in which the conductive paste 320 is filled in the entire through hole 73 without protruding upward is realized (see FIG. 7 (d)). That is, the conductive electrode 76 made of the conductive paste 320 is provided throughout the through hole 73 (FIG. 8).

  As is apparent from the above description, the process of forming the conductive electrode 76 in this embodiment, that is, the process of filling the through-hole 73 with the conductive paste 320 without excess or deficiency, is performed once by the first squeegee 203a. It is not intended to achieve this by operation alone. It is assumed that the conductive paste 320 contracts during the subsequent squeegee operation by the second squeegee 204a and the subsequent drying and pressing processes, and after that, the ideal conductivity without excess or deficiency. This is characteristic in that the filling state of the paste 320 is intended to be realized. Therefore, the thickness of the metal mask 310, the contact angle and hardness of the first squeegee 203a and the second squeegee 204a, the viscosity of the conductive paste, the moving speed of each squeegee, and the drying / pressing conditions are all This is defined as a requirement for suitably realizing the filling state.

  Specifically, when the first squeegee 203a fills the through hole 73 with the conductive paste 320, it is necessary to form a protruding portion after sufficient filling. The conditions (contact angle, hardness, moving speed, etc.) of the first squeegee 203a and the conditions that the viscosity of the conductive paste 320 are 4000 Pa · s or more are determined to satisfy these conditions.

  For example, when the viscosity of the conductive paste 320 is less than 4000 Pa · s, even when the conductive paste 320 is filled into the through hole 73, the above-described protruding portion is not formed. The surface of the conductive electrode 76 may become a recess. In such a case, there arises a problem that good conduction cannot be obtained with a contact pattern formed thereafter. In addition, since the conditions of the first squeegee 203a itself are inappropriate, the same problem occurs when the conductive paste 320 is scraped off more than necessary.

  On the other hand, the scraping by the second squeegee 204a needs to be performed so that the conductive paste 320 protrudes to the extent that a good filling state is realized by subsequent drying / pressing shrinkage. The conditions of the thickness of the metal mask 310 of 40 μm to 60 μm, the conditions of the second squeegee 204a (contact angle, moving speed, etc.) and the condition that the viscosity of the conductive paste 320 is 8000 Pa · s or less should be satisfied. It is determined.

  For example, if the metal mask 310 is too thin, the conductive paste 320 is scraped off more than necessary by the second squeegee 204a, and the surface of the conductive electrode 76 is depressed after the drying / pressing process. On the other hand, when the metal mask 310 is too thick or when the hard conductive paste 320 having a viscosity exceeding 8000 Pa · s is used, the second squeegee 204a cannot sufficiently scrape the conductive paste 320. More than necessary, the conductive paste 320 may remain as protrusions. The same problem may occur because the conditions of the second squeegee 204a itself are inappropriate.

  In the case where the conductive paste 320 is preferably filled into the through hole 73 only by squeegee operation in one direction, that is, without subsequent scraping operation, it is assumed that the pressing process is performed. However, it is necessary to suddenly realize the filling state as shown in FIG. 7C and the state shown in FIG. 7D when the pressing process is not performed. For this purpose, the inventors of the present invention have confirmed that it is necessary to maintain the viscosity of the conductive paste 320 in the range of about 3000 Pa · s to 4000 Pa · s. This means that the viscosity control is very severe compared to the condition of 4000 Pa · s to 8000 Pa · s in the present embodiment described above. In other words, it can be said that the method according to the present embodiment is a technique in which the allowable range of the viscosity of the conductive paste is wide and the viscosity can be easily managed.

  As described above, in the conductive electrode printing method according to the present embodiment, the conductive paste 320 is filled into the through hole 73 by the first squeegee 203a, and the conductive paste 320 is formed on the through hole 73. After depositing in a protruding shape, the second paste squeegee 204a scrapes the conductive paste 320 at the protruding portion to the extent that the conductive paste 320 is filled into the through-hole 73 without any excess by subsequent drying and pressing processes. Thus, a conductive electrode 76 having a good shape can be formed. Moreover, since the allowable range of the viscosity of the conductive paste is larger than when the conductive electrode is formed by a single squeegee operation, this is superior in terms of easy viscosity management.

<Printing method of connector pattern>
Next, a method for printing the connector pattern 330 on the green sheet 300 on which the conductive electrode 76 is formed will be described. The connector pattern 330 is a pattern of the heater electrode 71 or the heater end portions 72a and 72b.

  FIG. 9 is a diagram illustrating a state of the upper surface of the green sheet 300 after the conductive electrode 76 is formed by performing the pressing process. According to the method described above, the conductive electrode 76 having a good shape is formed. However, depending on the formation mode of the conductive electrode 76, as shown in FIG. 9, on the surface of the green sheet 300 after the pressing process, A blur 323 having a thickness of about 4 to 5 μm may be generated on the outer peripheral portion of the through hole 73. Such bleeding 323 is likely to occur when, for example, the through hole 73 is formed near the end of the green sheet 300.

  FIG. 10 is a schematic diagram showing how the bleeding 323 is formed in such a case. When the through hole 73 to be the conductive electrode 76 is formed at the end of the green sheet 300, the through hole 311 of the metal mask 310 is also formed at the end of the metal mask 310 correspondingly. The metal mask 310 is less likely to bend when the second squeegee 204a is moved to the end than when the first squeegee 203a is moved from the center of the metal mask 310 to reach the end of the metal mask 310. Therefore, in the former case, even if the metal mask 310 and the green sheet 300 are in good contact as shown in FIG. 10A, in the latter case, as shown in FIG. In addition, the metal mask 310 may be slightly lifted from the green sheet 300, and the conductive paste 320 may enter the gap (reference numeral) between the two. This is the cause of bleeding 323.

  If the bleeding 323 remains even after the connector pattern 330 is printed, there is a possibility that poor appearance or poor conduction may occur. Therefore, in the present embodiment, such a bleed 323 is used as a part of the connector pattern 330 so that such a problem does not occur. Below, the printing method of the connector pattern 330 is demonstrated.

  First, as described above, the conductive electrode 76 is formed prior to the printing of the connector pattern 330. The longitudinal direction of the connector pattern 330 formed after the green sheet 300 is the moving direction (x-axis direction) of the first squeegee 203a. This is performed after being placed and fixed on the table 201 so as to match. This is because, due to the mechanism described above, the formation position when the bleeding 323 is formed is on the positive side of the through-hole 73 in the x-axis direction, so that the formation position of the bleeding 323 is matched with the formation direction of the contact pattern 330. Because.

  When the conductive electrode 76 is formed by the above-described method, the connector pattern 330 (first connector pattern 331) is printed on the green sheet 300 in such a manner that the printing direction coincides with the longitudinal direction. For the printing of the first connector pattern 331, a known screen technology can be used by using a noble metal such as platinum or a refractory metal paste such as tungsten or molybdenum (the same applies to the second connector pattern). FIG. 11 is a view illustrating a state of the upper surface of the green sheet 300 after the first connector pattern 331 is printed. By printing the connector pattern 331, the bleeding 323 becomes a part of the connector pattern 331, and the difference in thickness between the region where the bleeding 323 occurs in the connector pattern and the other region is alleviated.

  Next, the connector pattern 330 (second connector pattern 332) is printed again on the first connector pattern 331. FIG. 12 is a diagram illustrating a state of the green sheet 300 after the second connector pattern 332 is printed. By printing the connector pattern 332, the thickness between the region where the bleeding 323 is generated in the connector pattern and the other region becomes substantially the same.

  That is, by printing the connector pattern 330 twice, the bleeding 323 becomes a part of the connector pattern. As a result, occurrence of poor appearance and poor conduction due to bleeding 323 generated outside the through hole 73 is prevented.

  As described above, according to the present embodiment, the conductive electrode 76 can be formed in a good shape inside the through hole 73 by printing the conductive electrode 76 by performing squeegee processing twice. In addition, even when the bleeding 323 is generated outside the through hole 73, the appearance 323 or the conduction caused by the bleeding 323 is caused by using the bleeding 323 generated outside the through hole 73 as a part of the connector pattern. The occurrence of defects is prevented.

<Example>
The appearance inspection and the warpage inspection of the connector pattern were performed on the green sheet A having the conductive electrodes printed by the printing method according to the present embodiment and the green sheet B which is a comparative example. The green sheet B is a conventional green sheet in which a conductive electrode is printed in a through hole by a single squeegee process. At this time, the squeegee has a contact angle of 45 °, and the conductive paste has a viscosity of 3500 ± 500 Pa · s.

  In the appearance inspection, metal jump inspection, embedded dent inspection, embedded blur inspection, and foreign matter adhesion inspection were performed. The metal jump inspection is an inspection in which, after performing the squeegee treatment, whether or not a short-circuit between terminals is caused by the conductive paste scattered around the through hole is confirmed visually or using a microscope. The embedded dent inspection is an inspection to check whether the printed conductive electrode is recessed from the green sheet surface by visual inspection after squeegee processing and image inspection after the heater layer is generated. is there. The embedded bleeding inspection is an inspection for visually confirming whether or not a short circuit between terminals is caused by the conductive paste that has spread around the through hole after the squeegee treatment. The foreign matter adhesion inspection is an inspection for visually confirming whether or not the upper part of the conductive electrode is scattered and a short circuit between the terminals occurs after the pressing process.

  The warpage inspection of the connector portion is an inspection for confirming whether or not the connector pattern is warped by measuring a deviation from a reference value with a laser displacement meter after printing the connector pattern.

  FIG. 13 is a diagram showing the inspection results of green sheet A and green sheet B. FIG. The number of measurements was 1000 sheets. As shown in FIG. 13A, it was confirmed that the green sheet A had a lower appearance defect rate than the green sheet B. Moreover, as shown in FIG.13 (b), it was confirmed that the green sheet A has the average value of a connector curvature smaller than the green sheet B, and its process capability is high. This result means that the gas sensor A can print a better conductive electrode than the gas sensor B.

  From the above results, it was confirmed that the use of the conductive electrode printing method according to the present embodiment is effective in forming a good conductive electrode.

73 through hole 76 conductive electrode 100 gas sensor 101 sensor element 200 embedded printing apparatus 201 table 202 fixing member 203 first squeegee unit 203a first squeegee 204 second squeegee unit 204a second squeegee 205 driving means 206 control means 300 green sheet 310 metal mask 320 Conductive paste 330 Connector pattern

Claims (4)

A method of printing a conductive electrode in a through hole provided in a green sheet and having an opening diameter of 300 μm to 900 μm and a depth of 100 μm to 800 μm ,
(A) fixing the green sheet on the table;
(B) a step of fixing a metal mask having a thickness of 40 μm to 60 μm and having a through hole by positioning the through hole and the through hole with a gap on the green sheet;
A first squeegee (c) hardness of 60 ° or less, the pressing Shinano the metal mask while maintaining a contact angle to the metal mask 15 ° to 45 ° is et previous SL below 30 mm / sec along the metal mask By moving at a moving speed, the through-hole is filled with a conductive paste having a viscosity of 4000 Pa · s to 8000 Pa · s supplied on the metal mask at room temperature , and from above the through hole. Depositing the conductive paste on the top;
(D) a second squeegee, said the pressing Shinano the metal mask while maintaining a contact angle to the metal mask 30 ° to 75 ° moves following the movement speed 50 mm / sec along the et before Symbol metal mask Scraping a part of the conductive paste deposited on the through-hole,
(E) drying the conductive paste;
(F) pressing the green sheet from above and below,
In the step (d), after the steps (e) and (f), the conductive paste is scraped off so that the conductive paste is filled into the through hole without excess or deficiency. A method for printing a conductive electrode. (G) After the step (f), further comprising a step of printing a connector pattern on the green sheet so as to include the through hole,
The said sheet | seat is fixed on the said table so that the longitudinal direction of the said connector pattern and the direction to which a said 1st squeegee moves may correspond in the said process (a). Printing method of the conductive electrode.   The said process (g) is a conductive electrode printing method of Claim 2 which prints the same connector pattern twice. The said process (a) fixes the said green sheet to the said table, after laying PET tape so that the area | region in which the said through hole was provided may be included at least among the back surfaces of the said green sheet. 4. The method for printing a conductive electrode according to any one of 3 above.