JP2007266353A - Method of manufacturing multilayer ceramic substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To reliably eliminate a defect produced in the periphery of an internal conductor in a multilayer ceramic substrate having the internal conductor. <P>SOLUTION: In a method of manufacturing a multilayer ceramic substrate, a conductor pattern made of a conductor paste is formed on at least some of a plurality of glass ceramic green sheets, and they are laminated and burned after their binder is removed. The amount of carbon remaining in the laminate after removing of the binder is set at a value not smaller than 0.01% in the conductor paste and not larger than 5% in the glass ceramic green sheet. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a multilayer ceramic substrate having an internal conductor such as a via-hole conductor, for example, and more particularly to a technique for preventing defects around the internal conductor.

  In the field of electronic equipment and the like, substrates for mounting electronic devices are widely used. However, in recent years, as a substrate having high reliability in response to demands for reduction in size and weight of electronic devices and multifunctional functions. A multilayer ceramic substrate has been proposed and put into practical use. The multilayer ceramic substrate is formed by laminating a plurality of ceramic layers, and high-density mounting is possible by integrally forming a wiring conductor, an electronic element, and the like in each ceramic layer.

  The multilayer ceramic substrate is formed by laminating a plurality of green sheets to form a laminate, then removing the binder and firing the laminate. The green sheet is surely contracted with the sintering in the firing step or the like, which is a major factor for reducing the dimensional accuracy of the multilayer ceramic substrate. Specifically, shrinkage variation occurs with the shrinkage, and the finally obtained multilayer ceramic substrate has a dimensional accuracy of about 0.5%.

  Under such circumstances, a so-called non-shrinkage firing method that suppresses shrinkage in the in-plane direction of the green sheet and shrinks only in the thickness direction in the firing process of the multilayer ceramic substrate has been proposed (for example, Patent Document 1). Etc.). As described in Patent Document 1 and the like, when a sheet that does not shrink even at the firing temperature is attached to a laminate of green sheets and firing is performed in this state, shrinkage in the in-plane direction is suppressed, and the thickness direction Only shrinks. According to this method, it is possible to improve the dimensional accuracy in the in-plane direction of the multilayer ceramic substrate to, for example, about 0.05%.

  By the way, in a multilayer ceramic substrate, it is essential to form an internal conductor such as a via-hole conductor for interlayer connection. When producing the multilayer ceramic substrate, for example, a via hole is formed and filled with a conductor paste. Firing is performed. In this case, it is known that voids (defects) are generated around the inner conductor (for example, via-hole conductor) due to a difference in heat shrinkage behavior between the conductor paste and the green sheet. Such a defect is particularly noticeable in the non-shrinkage firing method.

Thus, techniques for eliminating such defects have been studied in various fields (see, for example, Patent Documents 2 and 3). For example, in the invention described in Patent Document 2, by using a conductive composition for a multilayer ceramic substrate containing a conductive powder such as Ag and a Mo compound or a Mo metal as the conductor composition filled in the via hole, This makes it possible to produce a multilayer ceramic substrate that does not cause defects in the vicinity of the electrode after firing. Similarly, in the invention described in Patent Document 3, the via hole conductor is composed of Ag and W, so that no gap is generated between the via hole conductor and the inner wall of the via hole.
JP-A-10-75060 JP 2003-133745 A Japanese Patent No. 2732171

  However, as a result of repeated studies by the present inventors, it is not always possible to obtain satisfactory results only by controlling the shrinkage behavior of the conductive paste itself for forming the internal conductor as described in each of the above patent documents. In particular, it has been found that defects generated around the inner conductor cannot be sufficiently suppressed when a multilayer ceramic substrate is produced by the non-shrinkage firing method.

  The present invention has been proposed in view of such a conventional situation, and in a multilayer ceramic substrate having an inner conductor, it is possible to surely eliminate defects generated around the inner conductor, thereby providing a highly reliable multilayer ceramic substrate. It aims at providing the manufacturing method of the multilayer ceramic substrate which can manufacture a board | substrate.

  The present inventors have made various studies over a long period of time in order to achieve the aforementioned object. As a result, it came to the conclusion that the occurrence of the defects can be effectively suppressed by performing the binder removal so that the residual carbon amounts of the conductor paste and the glass ceramic green sheet are included in the specific ranges, respectively. . The present invention has been completed based on such findings.

  That is, in the method for producing a multilayer ceramic substrate of the present invention, a multilayer ceramic substrate is formed by forming a conductive pattern made of a conductive paste on at least a part of a plurality of glass ceramic green sheets, laminating and debinding the conductive pattern. And the binder removal is performed so that the amount of residual carbon after the binder removal is 0.01% or more in the conductor paste and 5% or less in the glass ceramic green sheet. Features.

  If organic components remain in the glass ceramic green sheet during firing of the multilayer ceramic substrate, this will rapidly gasify during the firing process and cause defects such as substrate swelling and warping. Therefore, the binder is removed before firing. There is a need. Here, for example, in the non-shrinkage firing method using a constraining layer, it is effective to remove the binder sufficiently in a range where delamination does not occur in the laminate.

  However, as a result of studies by the present inventors, when firing is performed after the binder is sufficiently debindered as in the past, the conductor contracts greatly in a certain temperature range (for example, 500 ° C. to 750 ° C.) during the firing process. On the other hand, the phenomenon that the glass ceramic green sheet hardly expands and contracts has occurred, and it has been found that the defects (voids) are generated at the interface between the glass ceramic and the conductor due to the difference in heat shrinkage behavior.

  Therefore, in the present invention, by removing the binder under the condition that the amount of residual carbon in the conductor paste is 0.01% or more, the heat shrinkage of the conductor in the firing process is suppressed, and the generation of the voids is suppressed. Yes. Here, if the binder is removed so that the organic component is intentionally left in the conductor paste, the organic component also remains in the glass ceramic green sheet. However, the organic component remains in the glass ceramic green sheet after the binder removal. If a large amount of components remain, the residual organic components are rapidly gasified during the firing process, which causes defects such as voids and substrate swelling. Therefore, the binder is removed so that the residual carbon content of the glass ceramic green sheet after the binder removal is 5% or less. By performing the binder removal under such conditions, generation of defects in the multilayer ceramic substrate is reliably suppressed.

  According to the present invention, it is possible to suppress the generation of voids at the interface between the inner conductor and the glass ceramic layer, and it is possible to reliably eliminate defects that occur around the inner conductor. Therefore, according to the present invention, it is possible to manufacture a multilayer ceramic substrate having no defects and high reliability.

  Hereinafter, a method for producing a multilayer ceramic substrate to which the present invention is applied will be described in detail with reference to the drawings.

  As shown in FIG. 1, a multilayer ceramic substrate 1 to be manufactured in the present invention is formed by laminating a plurality of glass ceramic layers 2 (here, four glass ceramic layers 2a to 2d), and these glass ceramic layers 2a to 2d. An internal conductor such as a via-hole conductor 3 penetrating 2d or a surface conductor 4 formed on both surfaces of the glass ceramic layers 2a to 2d is provided.

Each glass ceramic layers 2a~2d are those formed by firing plus the composite oxide such as alumina (Al 2 _{O 3)} having a predetermined glass composition. Here, as the respective oxides constituting the composite oxide having the glass composition, SiO ₂ or _{B 2 O 3, CaO, SrO} , BaO, La 2 O 3, ZrO 2, TiO 2, MgO, ZnO, PbO, Li ₂ O, Na ₂ O, K ₂ O, and the like can be given, and these may be used in appropriate combination. By making each ceramic layer constituting the multilayer ceramic substrate 1 the glass ceramic layer, firing at a low temperature becomes possible.

  On the other hand, the via-hole conductor 3 among the internal conductors is formed in such a manner that the via hole formed in each of the glass ceramic layers 2a to 2d is filled with a conductive material remaining by firing of the conductive paste. Thus, the surface conductors 4 formed on the ceramic layers 2a to 2d are electrically connected to each other and functions to conduct heat are performed. The cross-sectional shape of the via-hole conductor 3 is generally circular, but is not limited to this, and in order to obtain a large cross-sectional area in a limited shape space range, for example, an elliptical shape, an oval shape, a square shape, etc. can do.

Hereinafter, a method for manufacturing the multilayer ceramic substrate 1 will be described.
In order to produce a multilayer ceramic substrate, first, as shown in FIG. 2A, glass ceramic green sheets 11a to 11d to be glass ceramic layers after firing are prepared. The glass ceramic green sheets 11a to 11d are made of a slurry-like dielectric paste obtained by mixing the above-mentioned oxide powder and an organic vehicle, and this is used as a doctor blade on a support such as a polyethylene terephthalate (PET) sheet. It is formed by forming a film by a method or the like. Any known organic vehicle can be used.

  After the formation of the glass ceramic green sheets 11a to 11d, through holes (via holes) are formed at predetermined positions. The via hole is usually formed as a circular hole, and a conductor paste 12 is filled therein to form a via hole conductor. Further, a conductive paste is printed in a predetermined pattern on the surface of each glass ceramic green sheet 11 a to 11 d to form a surface conductor pattern 13.

  The conductive paste 12 used for forming the conductive paste 12 and the surface conductive pattern 13 filled in the via hole includes, for example, conductive materials made of various conductive metals and alloys such as Ag, Ag-Pd alloy, Cu, Ni, and organic vehicles. Is prepared by kneading.

  In the conductive paste, the organic vehicle is mainly composed of a binder and a solvent, and the mixing ratio of the conductive material is arbitrary, but the binder is usually 1 to 15% by mass, and the solvent is 10 to 50% by mass. It mix | blends with respect to an electrically-conductive material so that it may become. Additives selected from various dispersants, plasticizers and the like may be added to the conductor paste as necessary.

  Each glass ceramic green sheet 11a to 11d is filled with a conductor paste 12 serving as an internal conductor to form a surface conductor pattern 13, and then, as shown in FIG. In some cases, the shrinkage-suppressing green sheets 14 are disposed as constraining layers on both sides (outermost layers) of the laminate. FIG. 2B shows a so-called temporary stack state of a laminate, and then pressing is performed as shown in FIG.

  The shrinkage-suppressing green sheet 14 is made of a material that does not shrink at the firing temperature of the glass ceramic green sheets 11a to 11d, such as tridymite and cristobalite, quartz, fused quartz, alumina, mullite, zirconia, aluminum nitride, boron nitride, and oxide. A composition containing magnesium, silicon carbide, or the like is used, and the laminate is sandwiched between the shrinkage-suppressing green sheets 14 and fired to suppress shrinkage in the in-plane direction of the laminate.

  Thereafter, the binder removal and firing are sequentially performed. In the present invention, the binder removal is performed so that the residual carbon amount in the conductor paste is 0.01% or more and the residual carbon amount in the glass ceramic green sheet is 5% or less. I do.

  By firing the laminate with a predetermined amount of organic components remaining in the conductor paste after binder removal, the difference in heat shrinkage between the conductor and the glass ceramic green sheet during the firing process is eliminated, creating voids. Can be suppressed. When the binder is sufficiently removed so that the amount of residual carbon in the conductor is less than 0.01%, the conductor shrinks greatly in a certain temperature range (for example, 500 ° C. to 750 ° C.) while the glass ceramic is removed. Since expansion and contraction hardly occur in the above temperature range regardless of the binder condition, voids (defects) are generated at the interface between the conductor and the glass ceramic due to the difference in thermal contraction behavior. Therefore, the binder is removed so that the amount of residual carbon in the conductor paste is 0.01% or more.

  Further, when performing the binder removal, conditions are selected such that the amount of residual carbon in the glass ceramic green sheet is 5% or less. When the binder is removed so that the organic component remains in the conductor paste, a large amount of the organic component remains in other members of the laminate such as a glass ceramic green sheet and a shrinkage-suppressing green sheet. If the amount of residual carbon in the glass ceramic green sheet exceeds 5%, a large amount of organic components remaining in the firing process are rapidly gasified, resulting in inconveniences such as voids in the glass ceramic and substrate swelling. Arise. Therefore, in order to avoid the inconvenience, the binder removal is performed so that the amount of residual carbon in the glass ceramic green sheet is 5% or less.

  In order to ensure that the residual carbon amount in the conductor paste after debinding and the residual carbon amount in the glass ceramic green sheet are included in the above range, the binder removal conditions such as binder removal temperature and binder removal time should be controlled. More specifically, it is preferable to control the binder removal temperature. Since the binder removal temperature for making the residual carbon amount in the conductor paste and the residual carbon amount in the glass ceramic green sheet within the scope of the present invention varies depending on the decomposition temperature of the added organic component, etc., the conductor paste and What is necessary is just to determine suitably considering the composition of a glass ceramics green sheet, etc.

  For example, the conductive paste contains ethyl cellulose as a binder, bis (2-ethylhexyl) phthalate (DOP) as a plasticizer, and the glass ceramic green sheet uses an acrylic resin as a binder and butylphthalylbutyl as a plasticizer. When glycolate (BPBG) is contained, the binder removal temperature is preferably set to 220 ° C to 280 ° C. In this case, the residual carbon content in the glass ceramic green sheet after the binder removal can be reduced to 5% or less by setting the binder removal temperature to 220 ° C. or higher, and the binder removal temperature can be reduced to 280 ° C. or lower. The residual carbon content in the subsequent conductor paste can be made 0.01% or more.

  Further, the conductive paste contains polyvinyl butyral (PVB) as a binder, bis (2-ethylhexyl) phthalate (DOP) as a plasticizer, and the glass ceramic green sheet contains polyvinyl butyral (PVB) as a binder. When bis (2-ethylhexyl) phthalate (DOP) is contained as a plasticizer, the binder removal temperature is preferably set to 250 ° C to 340 ° C.

  After the binder removal, firing is further performed as shown in FIG. After firing, the glass ceramic green sheets 11a to 11d become glass ceramic layers 2a to 2d, and the conductive paste 13 in the via hole becomes the via hole conductor 3. Similarly, the surface conductor pattern 14 also becomes the surface conductor 4.

  After firing, as shown in FIG. 2E, the shrinkage-suppressing green sheet 14 is naturally peeled due to the difference in thermal expansion, and the multilayer ceramic substrate 1 of the present invention is obtained. In the obtained multilayer ceramic substrate 1, no defects are generated around the inner conductor (via-hole conductor 3 or surface conductor 4), and a highly reliable multilayer ceramic substrate can be realized.

  When the binder is removed under such a condition that the residual carbon content of the conductor is less than 0.01%, the internal conductor (for example, a conductor filled in the via hole) is present in a certain temperature range (for example, 500 ° C. to 750 ° C.) during the firing process. While the ceramic substrate shrinks greatly, the ceramic substrate hardly contracts, so that a gap is formed at the interface between the conductor and the ceramic substrate. In the case where green sheets for shrinkage suppression are arranged on both sides of the glass ceramic green sheet, if the temperature is further increased (for example, 800 ° C. to 900 ° C.), the ceramic substrate shrinks in the Z direction, but the shrinkage suppressing green The sheet does not shrink in the XY direction due to the action of the sheet. Therefore, the gap is not filled, resulting in defects in the multilayer ceramic substrate. When the shrinkage-suppressing green sheet is not used, the ceramic substrate shrinks evenly in the XYZ direction when the temperature is further raised during the firing process, so the gap is relatively easy to fill, but in order to completely suppress the occurrence of defects It does n’t come.

  On the other hand, in the present invention, by controlling the residual carbon amount in the conductor paste and the glass ceramic green sheet with a binder, the gap due to the contraction of the conductor in a certain temperature range (for example, 500 ° C. to 750 ° C.) of the firing process. Occurrence can be suppressed. For this reason, even if it is a case where the shrinkage | contraction suppression green sheet is used, generation | occurrence | production of the defect around an internal conductor can be suppressed reliably.

  The defect prevention effect is large when the above-described shrinkage-suppressing green sheet 14 is disposed and fired without shrinkage, but the present invention is not limited to this, and the same is true when the shrinkage-suppressing green sheet is not used. The effect of can be obtained.

  Hereinafter, specific examples to which the present invention is applied will be described based on experimental results.

<Void generation rate depending on binder removal temperature conditions>
The void generation rate in the multilayer ceramic substrate after firing due to the difference in binder removal conditions was investigated.
A through hole is formed in a glass ceramic green sheet, filled with a conductor paste serving as a via-hole conductor, a plurality of glass ceramic green sheets are laminated, and a green sheet for restraining shrinkage (restraint) on both sides of the laminated glass ceramic green sheet. Layer green sheet).

The glass ceramic green sheet contains glass powder, alumina powder, acrylic resin, and butylphthalyl butyl glycolate (BPBG). The compounding ratio in the glass powder is 52.4 wt% for SiO ₂ , 3.5 wt% for B ₂ O ₃ , 11.5 wt% for Al ₂ O ₃ , 1.7 wt% for MgO, 3.2 wt% for CaO, SrO Is 27.7 wt%. The constraining layer green sheet contains tridymite powder, quartz powder, acrylic resin, and BPBG. The conductive paste contains silver powder, glass powder, ethyl cellulose, and bis (2-ethylhexyl) phthalate (DOP). Table 1 shows the compositions and mixing ratios of the glass ceramic green sheet, constrained layer green sheet, and conductor paste.

  The resulting laminate was debindered. When the binder was used, the maximum temperature (the binder removal temperature) was changed as shown in FIG. When removing the binder, the rate of temperature rise is 3 ° C./min from room temperature to 180 ° C., 0.67 ° C./min from 180 ° C. to the maximum temperature, the maximum temperature holding time is 1 hour, and the air flow rate is 2 L. / Min. For each binder condition, the amount of residual binder in the laminate after debinding was examined. Here, the residual binder amount is the residual amount of organic components in the laminated body at the end of the binder removal, and the laminated body relative to the total of the mass reduced amount after binder removal and the mass reduced amount after firing of the laminated body. The amount of mass reduction after binder removal is expressed as a percentage.

  After removing the binder, firing was performed to obtain a multilayer ceramic substrate. Firing was performed under the conditions of a temperature rising rate of 20 ° C./min, a maximum temperature of 900 ° C., a holding time of 30 minutes, and an air flow rate of 2 L / min. The void generation rate in the multilayer ceramic substrate after firing was examined. Of the 100 multilayer ceramic substrates under each condition, the ratio of the number of voids observed by microscopic observation was defined as the void generation rate. FIG. 3 shows the relationship between the binder removal temperature and the void generation rate.

  It can be seen from FIG. 3 that the amount of binder remaining in the laminated body after the binder removal decreases as the binder removal is performed at a higher temperature. It can be seen that the void generation rate in the multilayer ceramic substrate decreases as the binder removal temperature increases, but the void generation rate increases conversely on the higher temperature side near the binder removal temperature of 250 ° C. Note that when the binder removal temperature was set to around 310 ° C. or higher, delamination occurred in the fired multilayer ceramic substrate.

<Sintering behavior after binder removal>
Here, the heat shrinkage behavior of the conductor paste and the glass ceramic green sheet after the binder removal was analyzed as a model. For the sintering behavior, an analytical sample made of a conductive paste and an analytical sample made of a glass ceramic green sheet were prepared, and the binder was removed under one of conditions of 250 ° C. for 1 hour, 280 ° C. for 1 hour, and 300 ° C. for 1 hour. And then analyzed by thermomechanical analysis (TMA). Moreover, the sintering behavior was also analyzed for the sample that was not subjected to binder removal. The result of the conductive paste is shown in FIG. 4, and the result of the glass ceramic green sheet is shown in FIG.

  As shown in FIGS. 4 and 5, glass ceramics show almost no difference in heat shrinkage behavior regardless of binder removal conditions. On the other hand, the shrinkage of the conductor in the range of 500 ° C. to 750 ° C. increases as the binder is removed at a high temperature. From the above, in the laminated body debindered at a high temperature such as 300 ° C., the sintering suppressing effect due to the organic component is lost, and only the conductor shrinks first, resulting in the generation of voids at the interface with the glass ceramic substrate. As shown in FIG. 3, it is estimated that the void generation rate increases.

<Change in residual carbon amount due to binder removal temperature by member>
Below, the optimal residual carbon amount after binder removal in the said conductor paste and the said glass-ceramics green sheet was examined. The residual carbon amount serves as an index of the residual amount of organic components in each member. An analytical sample made of a conductive paste and an analytical sample made of a glass ceramic green sheet were prepared, and a carbon sulfur analyzer (Horiba Seisakusho) This is a value analyzed using EMIA520). FIG. 6 shows the relationship between the binder removal temperature of each of the conductor paste and the glass ceramic green sheet and the amount of residual carbon after the binder removal, and the relationship between the binder removal temperature and the void generation rate.

  From FIG. 6, in order to suppress the generation of voids due to thermal shrinkage of the conductor paste at 500 ° C. to 750 ° C., the binder removal temperature needs to be 280 ° C. or less, and the binder removal condition (binder removal temperature) is It can be expressed as a residual carbon content of 0.01% or more in the conductor paste after binder removal. On the other hand, the binder removal temperature needs to be 220 ° C. or higher in order to prevent the generation of voids and the expansion of the substrate due to the rapid gasification of the organic components remaining in the glass ceramic green sheet. It can be seen that the amount of residual carbon in the glass ceramic green sheet is 5% or less. Table 2 shows the relationship between the amount of residual carbon after binder removal and the void generation rate. By setting the residual carbon content in the conductive paste to 0.01% or more and the residual carbon content in the glass ceramic green sheet to 5% or less, the void generation rate is suppressed to a low value.

<Examination with other glass ceramic green sheets and conductor paste>
In this experiment, the composition of the glass ceramic green sheet, the constraining layer green sheet and the conductor paste was changed as shown in Table 3, and the optimum binder removal conditions at this time were examined. As shown in Table 3, the conductive paste contains polyvinyl butyral (PVB) and bis (2-ethylhexyl) phthalate (DOP), and the glass ceramic green sheet contains polyvinyl butyral (PVB) and bis (phthalate) (2- Ethyl hexyl) (DOP).

  After producing a laminated body using the conductor paste having the composition shown in Table 3, the glass ceramic green sheet, and the constraining layer green sheet, the binder is removed and fired, and the residual carbon amount after the binder removal and the voids after firing are performed. The relationship with the incidence was examined. The results are shown in Table 4. Even when the glass ceramic green sheet and the conductive paste having the composition shown in Table 3 are used, the generation of voids can be suppressed by performing the binder removal so that the respective residual carbon amounts are within the range of the present invention. there were. In addition, in this composition, the binder removal temperature which makes residual carbon amount in the said range was 250 to 340 degreeC.

It is a schematic sectional drawing which shows an example of a multilayer ceramic substrate. It is typical sectional drawing which shows the manufacturing process of a multilayer ceramic substrate, (a) is a glass ceramics green sheet and internal conductor formation process, (b) is a temporary stacking process, (c) is a press process, (d) is a baking process. A process and (e) show the green sheet peeling process for shrinkage | contraction suppression. It is a characteristic view which shows the relationship between a binder removal temperature and the laminated body residual binder amount after a binder removal, and the relationship between a binder removal temperature and the porosity generation rate in the multilayer ceramic substrate after baking. (A) is a characteristic view which shows the sintering behavior of the conductor paste after a binder removal, (b) is a figure which expands and shows the range of 200 to 800 degreeC in (a). (A) is a characteristic view which shows the sintering behavior of the glass ceramic green sheet after a binder removal, (b) is a figure which expands and shows the range of 300 to 800 degreeC in (a). It is a characteristic view which shows the relationship between the binder removal temperature and the amount of residual carbon after the binder removal of the conductor paste and the glass ceramic green sheet, and the relationship between the binder removal temperature and the void generation rate in the multilayer ceramic substrate after firing.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Multilayer ceramic substrate, 2a-2d glass-ceramics layer, 3 Via-hole conductor, 4 Surface conductor, 11a-11d Glass-ceramics green sheet, 12 Conductive paste, 13 Surface conductor pattern, 14 Shrinkage suppression green sheet

Claims (5)

A method for producing a multilayer ceramic substrate, comprising forming a conductive pattern made of a conductive paste on at least a part of a plurality of glass ceramic green sheets, laminating and debinding this, and then firing.
The multilayer ceramic substrate is characterized in that the binder removal is performed so that a residual carbon amount after the binder removal is 0.01% or more in the conductor paste and 5% or less in the glass ceramic green sheet. Production method.   2. The method for producing a multilayer ceramic substrate according to claim 1, wherein a shrinkage-suppressing green sheet is disposed on an outermost layer of the laminated glass ceramic green sheets, and the binder removal and the firing are performed.   The multilayer ceramic substrate according to claim 1 or 2, wherein a via hole is formed in at least a part of the plurality of glass ceramic green sheets, and the conductive pattern is filled in the via hole to form the conductive pattern. Manufacturing method.   When the conductor paste contains ethyl cellulose and bis (2-ethylhexyl) phthalate, and the glass ceramic green sheet contains an acrylic resin and butyl phthalyl butyl glycolate, the binder removal temperature is set to 220 ° C. The method for producing a multilayer ceramic substrate according to any one of claims 1 to 3, wherein the temperature is 280 ° C. When the conductor paste contains polyvinyl butyral and bis (2-ethylhexyl) phthalate, and the glass ceramic green sheet contains polyvinyl butyral and bis (2-ethylhexyl) phthalate, the binder removal The method for producing a multilayer ceramic substrate according to any one of claims 1 to 3, wherein the temperature is 250 ° C to 340 ° C.

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