JP2006121016A - Manufacturing method of electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide the manufacturing method of an electronic component with high dimension accuracy without delamination. <P>SOLUTION: The manufacturing method includes the steps of forming a conductor layer 2 on a support body 1; forming a first ceramic green sheet 3 on the support body 1 on which the conductor layer 2 is formed; forming a second ceramic green sheet 4; forming a lamination ceramic green sheet 5 comprising the conductor layer 2 and the first and second ceramic green sheets 3, 4, by laminating and heating the first and second ceramic green sheets 3, 4; forming a ceramic green sheet laminate 6 by laminating a plurality of the lamination ceramic green sheets 5; and sintering the ceramic green sheet laminator 6. The second ceramic green sheet 4 contains a melting component brought into a melting state in the case of the heating when the lamination ceramic green sheet 5 is manufactured, and the ceramic green sheet laminate 6 is manufactured. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for manufacturing an electronic component such as a multilayer capacitor or a multilayer ceramic wiring board.

  In recent years, with the miniaturization of electronic devices, there has been a demand for miniaturization and high performance in electronic components such as multilayer capacitors and multilayer ceramic wiring boards. For example, multilayer capacitors are required to have multilayered thin dielectric layers and conductor layers for miniaturization and high capacity. In addition, in a multilayer ceramic wiring board, a thinner insulating layer and a wiring conductor layer are formed in multiple layers in order to reduce the size and increase the density of the wiring conductor, and the wiring conductor layers are required to have finer widths and intervals. .

  Such electronic parts are made by adding an organic binder, plasticizer, solvent, etc. to ceramic powder to form a slurry, forming a ceramic green sheet (hereinafter also referred to as green sheet) with a doctor blade, etc., and then a conductor containing metal powder. A conductive layer is formed on the above-mentioned green sheet by printing a paste, etc., and then a green body on which a plurality of conductive layers are formed is laminated and pressed to obtain a laminated body. It is obtained by firing the body.

  When a large number of green sheets on which conductor layers are formed are laminated in response to demands for electronic components, the difference in thickness between a portion where the conductor layer is formed overlaps with a portion where the region does not overlap. For this reason, when the laminated green sheets are pressed in the thickness direction, the applied pressure is sufficiently applied in the portion where the regions where the conductor layers are formed overlap, but the applied pressure is not easily applied in the other portions. It tends to be insufficient crimping. As a result, when such a laminate is fired, there is a problem in that delamination (delamination) occurs at a portion where the pressure bonding is insufficient.

  When such delamination is present inside the electronic component, there is a problem in that electrical characteristics cannot be ensured because a change in electrical capacitance value or dielectric breakdown tends to occur.

  In order to solve such a problem, Patent Document 1 proposes to use a laminate having a highly fluid portion having high fluidity when pressurized. When the laminated body is pressed in the thickness direction, the high fluidity part existing in the area where the internal electrodes are laminated moves to the remaining part and the thickness of the remaining part increases to increase the pressure. Is uniformly added to the entire surface, so that delamination hardly occurs.

  In addition, when another green sheet is laminated on the conductor layer formed on the green sheet, the green sheet hardly follows the cross-sectional shape of the conductor layer, so that a void is generated around the conductor layer. There is a problem that delamination is likely to occur. In particular, when the distance between the conductor layers was fine, voids were easily generated between the conductor layers.

  In order to solve this problem, Patent Document 2 proposes that after a conductor layer is formed on a green sheet, a ceramic paste is printed in a region around the portion where the conductor layer is formed. If such a method is used, the step between the conductor layer and the green sheet can be eliminated by printing the ceramic paste in a region around the portion where the conductor layer is formed. For this reason, it is possible to suppress the generation of voids around the conductor layer and between the wiring conductor layers, and to suppress the occurrence of delamination caused by the voids. In addition, there is no difference in thickness even when a plurality of green sheets on which a conductor layer is formed are laminated, so that pressure can be applied without unevenness and crimping can be suppressed, and the occurrence of insufficient crimping can be suppressed. Generation of lamination can be suppressed.

Further, as described in Patent Document 3, a ceramic slurry is applied on a support on which a conductor is formed on the surface, dried and then peeled off, thereby removing a green sheet having a flat surface on which the conductor is formed. A forming method has been proposed. Similarly in this method, it is possible to suppress the occurrence of delamination caused by the gap between the wiring conductor layers and the delamination caused by the pressurization unevenness at the time of pressure bonding due to the thickness difference.
Japanese Patent No. 3344100 JP-A-5-217448 Japanese Patent Laid-Open No. 50-64768

  However, in the conventional method using a laminate having a high fluidity portion, a high pressure of 180 MPa, for example, is applied in the thickness direction in order to move the high fluidity portion and perform pressure bonding so that delamination does not occur. There is a need. When such a high pressure is applied to the green sheet on which the conductor layer is formed, the shape of the green sheet or the conductor pattern is deformed. As a result, the desired dimensional accuracy of the multilayer ceramic wiring board cannot be obtained, so it becomes difficult to mount components on the multilayer ceramic wiring board, and the conductor pattern shape as designed cannot be obtained. There has been a problem that electrical characteristics such as impedance matching cannot be obtained with a wiring board or the like. Furthermore, the problem of voids generated around the conductor layer when the interval between the conductor patterns is fine remains unsolved.

  Further, in the method of printing the ceramic paste on the area around the portion where the conductor layer is formed, not only the step of printing the ceramic paste on the green sheet on which the conductor layer is formed is added, but also a fine It is difficult to accurately align and print the conductor pattern, and it is difficult to print the ceramic paste between adjacent conductor layers, particularly when the distance between the conductor patterns is fine. For this reason, the ceramic paste is also printed on the conductor layer, and the ceramic paste printed on the conductor layer connects the through conductors to connect the conductor layers that are stacked and arranged one above the other. There was a problem of disappearing.

  Furthermore, in the method of forming a flat green sheet by applying a ceramic slurry on a support having a conductor formed on the surface, and then drying and peeling, it is necessary to apply a high pressure of 5 to 30 MPa in the laminating process. . When such a high pressure is applied to the green sheet, the shape of the green sheet or the conductor pattern is deformed. As a result, when producing electronic components, it is difficult to mount the components on the electronic components because the desired dimensional accuracy cannot be obtained, and the conductor pattern shape as designed cannot be obtained. There has been a problem that electrical characteristics such as impedance matching cannot be obtained with a wiring board or the like.

  Furthermore, when manufacturing an electronic component having a cavity, a green sheet formed with a through hole serving as a cavity and a green sheet not formed with a through hole serving as a bottom of the cavity are laminated and pressed. There was a problem that the cavity bottom of the laminate was warped. This is because pressure is applied only to the periphery of the cavity due to pressurization for pressure bonding, and the green sheet around the cavity extends due to pressurization, whereas no pressure is applied to the bottom of the cavity, so the green sheet at the bottom of the cavity By being pushed from. This is more likely to occur when the electronic component is smaller and the cavity bottom is thinner. If the cavity bottom warps, it becomes difficult to mount an electronic element such as a crystal resonator or an IC chip. Even if it can be mounted, the mounted components are tilted. Therefore, when an optical semiconductor element such as a CCD or C-MOS is mounted, there is a problem that the light receiving accuracy is deteriorated.

  The present invention has been completed in view of the above-described conventional problems, and an object of the present invention is to provide a method for manufacturing an electronic component that has no delamination and has high dimensional accuracy.

  The electronic component manufacturing method of the present invention includes a step of forming a conductor layer on a support, a step of forming a first ceramic green sheet on the support on which the conductor layer is formed, and a second ceramic green. A laminated ceramic green comprising the conductor layer and the first and second ceramic green sheets by stacking and heating the first ceramic green sheet and the second ceramic green sheet; A step of forming a sheet, a step of producing a ceramic green sheet laminate by laminating and heating a plurality of the laminated ceramic green sheets on which the conductor layers are formed, and a step of firing the ceramic green sheet laminate And the second ceramic green sheet comprises the multilayer ceramic green Characterized in that it contains a melting component as a molten state when heated at the time of making the time and the ceramic green sheet laminate to produce a sheet.

  In the present invention, the melting component preferably has a melting point of 35 to 100 ° C.

  In the present invention, it is preferable that the addition amount of the organic binder contained in the second ceramic green sheet is 19 to 25 parts by mass with respect to 100 parts by mass of the inorganic powder.

  In the present invention, it is preferable that the organic binder contained in the second ceramic green sheet has a molecular weight of 80,000 to 300,000.

  In the present invention, it is preferable that the acid value of the organic binder contained in the second ceramic green sheet is 0.1 to 0.8 KOHmg / g.

  In the present invention, it is preferable that the addition amount of the organic binder contained in the first ceramic green sheet is 8 to 20 parts by mass with respect to 100 parts by mass of the inorganic powder.

  In the present invention, it is preferable that the organic binder contained in the first ceramic green sheet has an average molecular weight of 50,000 to 800,000.

  In the present invention, it is preferable that the acid value of the organic binder contained in the first ceramic green sheet is 0.1 to 5 KOHmg / g.

  In the present invention, preferably, the glass transition point of the organic binder contained in the second ceramic green sheet is −20 to 0 ° C.

  In the present invention, it is preferable that the organic binder contained in the second ceramic green sheet has a hydroxyl value of 0.1 to 5 KOHmg / g.

  In the present invention, preferably, the glass transition point of the organic binder contained in the first ceramic green sheet is −20 to 10 ° C.

  In the present invention, it is preferable that the organic binder contained in the first ceramic green sheet has a hydroxyl value of 5 to 100 KOHmg / g.

  In the present invention, preferably, the heating in the step of producing the multilayer ceramic green sheet is performed at a temperature higher by 0 to 70 ° C. than the melting point of the molten component.

  According to the method for manufacturing an electronic component of the present invention, the method includes a step of forming a conductor layer on a support and a step of forming a first ceramic green sheet on the support on which the conductor layer is formed. Therefore, since the conductor layer is formed by being embedded in the first ceramic green sheet, the first ceramic green sheet is flat without a step of the conductor, and delamination caused by uneven pressure is caused. Occurrence can be suppressed. In addition, since the second ceramic green sheet contains a melting component that melts when heated, the first ceramic green sheet and the second ceramic green sheet produced separately are first laminated and heated. Since the second ceramic green sheet is softened when the multilayer ceramic green sheet is manufactured by the above, the second ceramic green sheet follows the surface shape of the first ceramic green sheet positioned above or below the second ceramic green sheet. Will be deformed. As a result, the first and second ceramic green sheets can be brought into close contact with each other without generating a gap between the first ceramic green sheet and the second ceramic green sheet.

  When the laminated ceramic green sheets are laminated and heated, the second ceramic green sheet softens, so that the second ceramic green sheet is positioned above and below the first ceramic green sheet and Deformation follows the surface shape of the conductor layer. As a result, the multilayer ceramic green sheets are brought into close contact with each other without generating voids around the conductor layer or between the conductor layers, and the electronic component obtained by firing the ceramic green sheet laminate is free from delamination. It will be a thing.

  Since the second ceramic green sheet contains a melting component that melts when heated, the second ceramic green sheet softens and has adhesiveness only by heating. There is no need to crimp ceramic green sheets. Furthermore, since the second ceramic green sheet does not soften and does not have adhesiveness at room temperature without heating, there is an advantage that handling is easy in processing without heating.

  And since the said 1st ceramic green sheet in which the said conductor layer is formed does not contain the fusion | melting component which fuse | melts at the time of a heating, the said 1st ceramic green sheet does not deform | transform at the time of a heating, The said laminated ceramic laminated | stacked In order to prevent the green sheets from being displaced from each other and to hold the softened second ceramic green sheet in order to assist in deformation following the surface shapes of the first ceramic green sheet and the conductor layer. It does not deform. Therefore, the shape of the multilayer ceramic green sheet and the conductor layer formed thereon is not deformed, and the obtained ceramic green sheet laminate and the electronic component obtained by firing it have high dimensional accuracy. Become.

  In addition, when the melting point of the melting component that is melted during heating is 35 ° C. to 100 ° C., the second ceramic green sheet does not soften and deform at room temperature, so handling up to the lamination process It is easier, and organic components such as the organic binder and plasticizer in the first and second ceramic green sheets are not decomposed during heating, so that delamination does not occur due to the decomposition gas, which is more preferable. It will be a thing.

  In addition, when the addition amount of the organic binder contained in the second ceramic green sheet is 19 to 25 parts by mass with respect to 100 parts by mass of the inorganic powder, the second ceramic green sheet is positioned above or below the second ceramic green sheet. Since it deforms following the surface shapes of the first ceramic green sheet and the conductor layer, it does not cause delamination or delamination between layers, and there is no distortion of the multilayer ceramic green sheet due to pressurization. Since the pressure bonding can be performed with a low applied pressure, the dimensional variation is small, which is more preferable.

  Further, if the molecular weight of the organic binder contained in the second ceramic green sheet is 80,000 to 300,000, the shape retention of the first ceramic green sheet is maintained, and the organic ceramic binder is contained in the second ceramic green sheet. The molten component is uniformly dispersed when melted by heating, and a sufficient amount of the molten component of the second ceramic green sheet can be maintained, so that there is no delamination or delamination between layers and green Since pressure bonding can be performed with such a low pressing force that there is no distortion to the sheet, dimensional variation is small, which is more preferable.

  In addition, when the acid value of the organic binder contained in the second ceramic green sheet is 0.1 to 0.8 KOHmg / g, the molten component contained in the second ceramic green sheet is melted by heating. And the laminated ceramic green sheet can be heated to maintain a sufficient amount of the molten component contained in the second ceramic green sheet, so that no delamination or delamination occurs between the layers. In addition, since the pressure bonding can be performed with such a low pressing force that there is no distortion to the multilayer ceramic green sheet due to pressurization, the dimensional variation becomes smaller, which is more preferable.

  Further, if the addition amount of the organic binder contained in the first ceramic green sheet is 8 to 20 parts by mass with respect to 100 parts by mass of the inorganic powder, the first and second ceramic green sheets are laminated and heated. When producing the multilayer ceramic green sheet by doing so, it is possible to suppress the diffusion of the molten component contained in the second ceramic green sheet to the first ceramic green sheet, and at the time of lamination Since the laminated ceramic green sheet can be heated to maintain a sufficient amount of the molten component contained in the second ceramic green sheet, it deforms following the surface shapes of the first ceramic green sheet and the conductor layer. Therefore, no delamination occurs and the ceramic Since it bonded at low pressure of about no distortion of the sheet is small dimensional variation becomes more preferable.

  If the molecular weight of the organic binder contained in the first ceramic green sheet is 50,000 to 800,000, the first and second ceramic green sheets are laminated and heated to heat the laminated ceramic green sheet. When producing, the molten component contained in the second ceramic green sheet can be prevented from diffusing into the first ceramic green sheet, and the laminated ceramic green sheet is heated during lamination to Since a sufficient amount of the molten component contained in the second ceramic green sheet can be maintained, it deforms following the surface shape of the first ceramic green sheet and the conductor layer, so that no delamination occurs. And there is no distortion to the multilayer ceramic green sheet due to pressure Since it bonded at lower pressure, small dimensional variations, and because good appearance state of the first ceramic green sheet becomes more preferable.

  If the acid value of the organic binder contained in the first ceramic green sheet is 0.1 to 5.0 KOHmg / g, the first and second ceramic green sheets are stacked and heated to stack the stacked layers. When producing a ceramic green sheet, the molten component contained in the second ceramic green sheet can be prevented from diffusing into the first ceramic green sheet, and the laminated ceramic green sheet is Heating can maintain a sufficient amount of the molten component contained in the second ceramic green sheet, and deformation occurs following the surface shape of the first ceramic green sheet and the conductor layer, resulting in delamination Without any distortion to the multilayer ceramic green sheet due to pressure. Since it pressed at a low pressure of, small dimensional variations, and because good appearance state of the first ceramic green sheet becomes more preferable.

  If the glass transition point of the organic binder contained in the second ceramic green sheet is −20 to 0 ° C., the shape-retaining property of the second ceramic green sheet is maintained and the laminated ceramic green is laminated. Since the sheet can be heated to maintain a sufficient amount of the melting component contained in the second ceramic green sheet and deforms following the surface shape of the first ceramic green sheet and the conductor layer, delamination Therefore, it is possible to press-bond with a pressurizing force as low as possible without causing distortion to the multilayer ceramic green sheet due to pressurization.

  In addition, when the hydroxyl value of the organic binder contained in the second ceramic green sheet is 0.1 to 5 KOHmg / g, it is uniform when the melting component contained in the second ceramic green sheet is melted by heating. And the laminated ceramic green sheet is heated at the time of lamination to maintain a sufficient amount of the molten component contained in the second ceramic green sheet, and the surfaces of the first ceramic green sheet and the conductor layer can be maintained. Since the deformation follows the shape, delamination does not occur and the multilayer ceramic green sheet can be pressure-bonded with such a low pressing force that there is no distortion.

  If the glass transition point of the organic binder contained in the first ceramic green sheet is −20 to 10 ° C., the first and second ceramic green sheets are laminated and heated to heat the laminated ceramic green. When a sheet is produced, adhesion, cracking and chipping of the multilayer ceramic green sheet can be prevented, which is more preferable.

  In addition, when the organic binder contained in the first ceramic green sheet has a hydroxyl value of 5 to 100 KOHmg / g, the inorganic powder and the organic binder contained in the first ceramic green sheet are uniformly dispersed. Therefore, the dimensional variation is small and the molten component contained in the second ceramic green sheet layer is deformed following the surface shapes of the first ceramic green sheet layer and the conductor layer during heating. There is no occurrence of lamination, which is more preferable.

  Further, by performing heating in the step of producing the multilayer ceramic green sheet at a temperature that is 0 to 70 ° C. higher than the melting point of the molten component, an appropriate amount from the second ceramic green sheet to the first ceramic green sheet is achieved. The molten component diffuses, the bonding strength at the interface between the second ceramic green sheet and the first ceramic green sheet is maintained, and when the second ceramic green sheet laminate is heated at the time of heating, The ceramic green sheet is softened only by heating, deforms following the surface shapes of the first ceramic green sheet and the conductor layer, and a sufficient amount of the molten component is added so as to have adhesiveness. 2 can be held in the ceramic green sheet.

  In addition, when manufacturing electronic parts having cavities, it is not necessary to press the ceramic green sheet with a large applied pressure, so the warping of the bottom of the cavity due to the difference in the elongation of the green sheet due to the pressurization between the cavity periphery and the cavity bottom. It is possible to suppress the generation, and it is possible to obtain an electronic component that can accurately and reliably mount the electronic element on the bottom of the cavity.

  As described above, according to the manufacturing method of the present invention, it is possible to obtain a ceramic green sheet laminate in which no gap is generated between the ceramic green sheets and the deformation of the ceramic green sheet or the conductor layer is suppressed. The electronic component produced by the manufacturing method of the invention has no delamination and becomes an electronic component having high dimensional accuracy.

  The method for manufacturing an electronic component of the present invention will be described in detail below.

  FIG. 1 is a cross-sectional view for each process showing an example of an embodiment of a method of manufacturing an electronic component according to the present invention, wherein 1 is a support, 2 is a conductor layer, 3 is a first ceramic green sheet, and 4 is a second. The ceramic green sheet 5 is a laminated ceramic green sheet (hereinafter, the ceramic green sheet is also referred to as CG), and 6 is a ceramic green sheet laminate.

  First, as shown in FIG. 1A, a conductor layer 2 is formed on a support 1. As a method of forming the conductor layer 2 on the support 1, for example, a method of forming a paste of conductor material powder (conductor paste) by printing such as screen printing, gravure printing, or ink jet printing, or , A method of processing a metal foil such as a plating method such as a semi-additive method or an additive method, a subtract method, a method of directly forming a metal film having a predetermined pattern shape such as a vapor deposition method, or a method of forming a predetermined pattern shape by printing There are methods of transferring the formed conductor thick film, a metal foil processed into a predetermined pattern shape, a metal film having a predetermined pattern shape formed by a plating method, a vapor deposition method or the like to the support 1.

  Examples of the conductive material include one or more of W, Mo, Mn, Au, Ag, Cu, Pd (palladium), Pt (platinum), etc., and in the case of two or more, mixing, alloy, coating Or any other form.

  In the present invention, when the conductor layer 2 is formed by a printing method, the conductor paste is a mixture of a conductor powder, an organic binder (hereinafter also referred to as a binder), a solvent, and the like. In order to adjust the hardness and strength of 2, a dispersant or a plasticizer may be added.

  Here, as the binder applied to the conductor paste, those conventionally used for conductor paste can be used. For example, acrylic (acrylic acid, methacrylic acid or ester homopolymer or copolymer) Polymer, specifically acrylic ester copolymer, methacrylic ester copolymer, acrylic ester-methacrylic ester copolymer, etc.), polyvinyl butyral, polyvinyl alcohol, acrylic-styrene, polypropylene Examples include carbonate-based and cellulose-based homopolymers or copolymers. In view of decomposition and volatility in the firing step, acrylic and alkyd binders are more preferable. The amount of the binder added varies depending on the shape and type of the conductor particles, but may be any amount that can disperse the conductor particles without any problem in the decomposability of the binder.

  Furthermore, the solvent applied to the conductor paste may be any solvent that can disperse and mix the conductor powder and binder, and plasticizers such as terpineol, butyl carbitol acetate, and phthalic acid. However, in consideration of the drying property of the solvent after the formation of the conductor layer 2, a low boiling point solvent such as terpineol is preferable.

  The support 1 in the present invention is not limited as long as it can form the conductor layer 2 and the first and second CGs 3 and 4, and conventionally used polyethylene terephthalate (hereinafter referred to as PET) or polybutylene terephthalate-isophthalate. Polyester resins such as polymers, polyolefin resins such as polyethylene, polypropylene, and polymethylpentene, polyfluorinated ethylene resins, cellulose resins, acrylic resins, and other paper-made supports such as fine paper and molded paper Can be used.

  In order to improve the peelability from the support 1 after the formation of the first and second CGs 3 and 4 on the surface of the support 1 on which the first and second CGs 3 and 4 are formed, surface treatment such as a release layer A layer may be formed. The types of release layers are broadly classified into silicone release agents and non-silicone release agents, and fluorine-based release agents can be used as the non-silicone release agents. As the release agent, any of a solventless type, an emulsion type, and a solvent type can be used depending on the product form. The thickness of the release layer varies depending on the type of release agent used, but the first and second CGs 3 and 4 can be peeled off from the support 1 and a conductor is formed using a conductor paste. In this case, the thickness of the conductive paste may be such that no repelling of the conductive paste occurs when the conductive layer 2 is formed by the release agent.

  When a conductor is formed on the support 1, the surface can be processed to form a rough surface in order to facilitate the formation of the conductor layer 2. Examples of the rough surface forming method include water jet, chemical blasting, sand blasting, wet blasting (a method of spraying abrasive grains and water by air pressure) and the like. Further, a method of forming a rough surface on the surface of the support by mixing and embedding pores or inorganic particles in the support can also be applied. The rough surface may be formed before or after the surface treatment layer is formed as long as the performance of the surface treatment layer such as the release layer can be maintained.

  Next, as shown in FIG.1 (b), 1st CG3 is produced on the support body 1 in which the conductor layer 2 was formed, and 2nd CG4 is produced on another support body, respectively. The first CG 3 and the second CG 4 can be obtained by a method in which a ceramic slurry in which ceramic powder, a binder, a solvent, and the like are mixed is formed by a doctor blade method, a lip coater method, a die coater method, or the like. In order to adjust the dispersibility of the ceramic powder and the hardness and strength of the CG, a dispersant or a plasticizer may be added. Moreover, 2nd CG4 contains the molten component which will be in a molten state at the time of a heating in the process of producing lamination | stacking CG5 and the CG laminated body 6. FIG.

  In addition to the present invention, as a method of forming the laminated CG5, a method of forming a second CG4 slurry on the first CG3 formed on the support 1 on which the conductor layer 2 is formed, The laminated CG5 can also be manufactured by a method in which the slurry of the second CG4 is applied on the slurry of the first CG3 applied on the support 1 on which the conductor layer 2 is formed. In this method, when forming the laminated CG5, there is a difference in solubility parameter between the first and second CGs 3, 4 or the slurry in order to prevent mixing and identification of the first and second CGs 3, 4 or the slurry. Must be set within range. On the other hand, in the method for manufacturing an electronic component according to the present invention, the first CG 3 and the second CG 4 are separately formed, laminated and heated to heat the conductor layer 2 and the first and second CG 3. Since the laminated CG5 composed of 4 is produced, the CG or ceramic slurry having a wider solubility parameter can be used without forming and mixing the same when forming the laminated CG5.

  The thickness of the first CG 3 is formed so as to be thicker than the thickness of the conductor layer 2 so as not to change the shape of the conductor layer 2 so that no gap is generated in the gap between the conductor layers 2. Further, as a method for producing the first CG 3 on the support 1 on which the conductor layer 2 is formed, the support 1 on which the conductor layer 2 is formed and the first CG 3 formed on another support are laminated. However, a method of transferring the conductor layer 2 to the first CG 3 by applying pressure or temperature and embedding the conductor layer 2 in the first CG 3 can also be applied. Compared with the case where the ceramic slurry is applied on the support on which the conductor layer 2 is formed, the conductor layer 2 is dissolved by the solvent in the ceramic slurry. Electrical characteristics such as poor electrical connection (open) and electrical short circuit (short) between the conductor layers 2 do not occur, which is more preferable.

Examples of the ceramic powder for obtaining the ceramic slurry include Al ₂ O ₃ , AlN, glass ceramic powder (mixture of glass powder and filler powder), etc., if it is a ceramic wiring board, and if it is a multilayer capacitor. Composite perovskite ceramic powders such as BaTiO ₃ system and PbTiO ₃ system are listed, and they are appropriately selected according to the characteristics required for electronic parts.

Examples of the glass component of the glass ceramic powder include SiO ₂ —B ₂ O ₃ system, SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ system, SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ —MO system (however, , M represents Ca, Sr, Mg, Ba or Zn), SiO ₂ —Al ₂ O ₃ —M ¹ O—M ² O system (where M ¹ and M ² are the same or different and Ca, Sr, Mg , Ba or Zn), SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ —M ¹ O—M ² O system (where M ¹ and M ² are the same as above), SiO ₂ —B ₂ O ₃ —M ³ ₂ O system (where M ³ represents Li, Na or K), SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ —M ³ ₂ O system (where M ³ is the same as above) Pb glass, Bi glass and the like.

Further, as the filler powder of the glass ceramic powder, for example, a composite oxide of Al ₂ O ₃ , SiO ₂ , ZrO ₂ and an alkaline earth metal oxide, a composite oxide of TiO ₂ and an alkaline earth metal oxide, A ceramic powder such as a composite oxide (for example, spinel, mullite, cordierite) containing at least one selected from Al ₂ O ₃ and SiO ₂ can be used.

  As the binder to be blended in the ceramic slurry, those conventionally used in the ceramic slurry can be used. For example, acrylic (a homopolymer or copolymer of acrylic acid, methacrylic acid or their esters, specifically, Acrylic ester copolymer, methacrylic ester copolymer, acrylic ester-methacrylic ester copolymer, etc.), polyvinyl butyral, polyvinyl alcohol, acrylic-styrene, polypropylene carbonate, cellulose Homopolymers or copolymers such as systems. In view of decomposition and volatility in the firing step, an acrylic binder is more preferable.

  The solvent is not particularly limited as long as the ceramic powder and the binder can be well dispersed and mixed, and examples thereof include organic solvents such as toluene, ketones, alcohols, and water. Among these, solvents having a high evaporation coefficient such as toluene, methyl ethyl ketone, and isopropyl alcohol are preferable because the drying step after slurry application can be performed in a short time.

  The molten component contained in the second CG 4 is a molten state when heated when the laminated CG 5 or the CG laminated body 6 is produced, and includes hydrocarbons, fatty acids, esters, fatty alcohols, polyhydric alcohols, and the like. It is done. Considering the solubility in a solvent when preparing the slurry, hydrocarbons, esters, fatty alcohols and polyhydric alcohols having a small molecular weight and polarity are preferred. Further, in view of compatibility with the above-described acrylic binder, esters, fatty alcohols, and polyhydric alcohols are more preferable.

  Among the above-mentioned melting components, those having a melting point of 35 to 100 ° C. are preferable. When a material having a melting point in this range is used, the second CG 4 is not softened and deformed at room temperature, so that the handling up to the lamination process is facilitated. Moreover, since organic components such as a binder and a plasticizer in the laminated CG 5 are not decomposed during heating in the process of manufacturing the CG laminated body 6, delamination due to decomposition gas does not occur. . Specific examples of the melting component having a melting point of 35 to 100 ° C. include hexadecanol, polyethylene glycol, polyglycerol, stearylamide, oleylamide, ethylene glycol monostearate, paraffin, stearic acid, and silicone.

  The content of the molten component contained in the second CG 4 varies depending on the binder component used and the amount thereof, and the molten component used, but the second CG 4 softens in a state where the molten component is melted, Any amount may be used so long as it is in contact with the first CG 3 of the laminated CG 5 positioned and the conductor layer 2 embedded therein without a gap.

  Moreover, it is preferable that the addition amount of the binder contained in 2nd CG4 is 19-25 mass parts with respect to 100 mass parts of inorganic powder. If the addition amount is lower than 19 parts by mass, when the first and second CGs 3 and 4 are laminated and heated, the second CG 4 is not sufficiently softened, and peeling between layers or inside the CG laminate 6 Delamination occurs. On the other hand, when the addition amount is higher than 25 parts by mass, when the second CG 4 is deformed, the entire laminated CG 5 is deformed, resulting in a large dimensional variation. In addition, when the CG laminate 6 is baked, the decomposition gas of the binder of the second CG 4 is excessively generated on the surfaces of the first CG 3 and the conductor layer 2, thereby generating blemish and delamination.

  The molecular weight of the binder contained in the second CG4 is preferably 80,000 to 300,000. When the molecular weight is lower than 80,000, the fluidity of the binder at room temperature becomes excessive, and the second CG4 is deformed and the shape retention cannot be obtained. Therefore, when the stacked CGs 5 are stacked to form the CG stacked body 6, when the stacked CGs 5 are stacked and heated, the dimensional variation of the CG stacked body 6 increases. Further, when the CG laminate 6 is fired, the decomposition gas of the binder of the second CG 4 is locally generated excessively on the surfaces of the first CG 3 and the conductor layer 2 by heating inside the laminate CG 5. And pinholes and delamination occur. When the molecular weight exceeds 300,000, the binders tend to be entangled with each other, causing aggregation of the binders and unevenness in the distribution of the molten component contained in the second CG4. For this reason, the dimensional variation of the CG laminate 6 becomes large, and when the first and second CGs 3 and 4 are laminated and heated, the second CG 4 is not sufficiently softened, peeling between layers, and laminating the laminated CGs 5 to each other. Then, when heated, a portion that does not soften occurs in the second CG 4, resulting in burr and delamination.

  The acid value of the binder contained in the second CG4 is preferably 0.1 to 0.8 KOHmg / g. When the acid value is lower than 0.1 KOHmg / g, the bonding property between the inorganic powder and the binder becomes weak, and non-uniform distribution such as aggregation of the inorganic powder and the binder occurs in the second CG4, resulting in melting. The components are unevenly distributed. When the laminated CG5 is laminated and heated, unevenness occurs in the softening of the second CG4 and does not change following the surface shapes of the first CG3 and the conductor layer 2 of another laminated CG5 ′ located below the second CG4. Locations occur, delamination and delamination occur between layers, and dimensional variation increases. When the acid value exceeds 0.8 KOH mg / g, the binder binding property becomes strong, so that the binder agglomerates and the distribution of the molten component becomes uneven. As a result, when the stacked CGs 5 are stacked and heated, a portion that is not softened is generated in the second CG 4, peeling between layers and delamination occur, and dimensional variation increases.

  Moreover, it is preferable that the addition amount of the binder contained in 1st CG3 is 8-20 mass parts with respect to 100 mass parts of inorganic powder. If the addition amount is less than 8 parts by mass, the density of the first CG 3 is low when the first and second CGs 3 and 4 are laminated and heated to produce the second CG 4. The molten component inside diffuses and the amount of the molten component necessary for the second CG 4 cannot be maintained. Therefore, when the stacked CGs 5 are stacked and heated, the second CG 4 is not softened and delamination occurs inside the CG stacked body 6. When the added amount is more than 20 parts by mass, the binder in the first CG3 diffuses into the second CG4 when the laminated CG5 is produced by laminating and heating the first and second CG3, 4. As a result, the molten component diffuses from the second CG 4 to the first CG 3, so that the necessary amount of the molten component cannot be maintained in the second CG layer. Therefore, when the stacked CGs 5 are stacked and heated, the second CG 4 is not softened and delamination occurs inside the CG stacked body 6.

  The molecular weight of the binder contained in the first CG3 is preferably 50,000 to 800,000. When the molecular weight is lower than 50,000, the molten component contained in the second CG4 diffuses into the first CG3 when the laminated CG5 is manufactured. Therefore, a sufficient amount of the molten component in the second CG4. When the CG laminate 6 is manufactured, the second CG 4 does not deform following the surface shapes of the first CG 3 and the conductor layer 2, and delamination occurs. When the molecular weight is higher than 800,000, the binding force between the binders becomes strong, and the raw material components contained in the first CG3 are not uniformly dispersed, so that appearance defects such as pinholes occur in the first CG3, This may cause insulation failure in the product.

  Further, when the acid value of the binder contained in the first CG3 is 0.1 to 5.0 KOHmg / g, when the acid value is lower than 0.1 KOHmg / g, the second CG5 is produced when the laminated CG5 is manufactured. Since the molten component contained in the CG4 diffuses into the first CG3, a sufficient amount of the molten component cannot be maintained in the second CG4, and when the CG laminate 6 is produced, Delamination occurs without deformation following the surface shapes of the first CG 3 and the conductor layer 2. When the acid value is higher than 5.0 KOHmg / g, the binding force between the binders becomes strong, and the raw material components contained in the first CG3 are not uniformly dispersed, so that poor appearance such as pinholes in the first CG3. Occurs, which causes insulation failure in the product.

  Moreover, it is preferable that the glass transition point of the binder contained in 2nd CG4 is -20 thru | or 0 degreeC. If the glass transition point is lower than −20 ° C., the fluidity of the binder at room temperature becomes excessive, so that the adhesion between the second CG4 occurs and handling becomes difficult, and the second CG4 is deformed by heating. In this case, the entire laminated CG5 is deformed and the dimensional variation increases. When the glass transition point is higher than 0 ° C., when the laminated CGs 5 are laminated and heated, the second CG 4 is not softened, and the laminated CG 5 is a first CG 3 and a conductor layer of another laminated CG 5 ′ located below the laminated CG 5. Since the shape does not change following the surface shape of No. 2, delamination occurs and dimensional variation increases.

  The hydroxyl value of the binder contained in the second CG4 is preferably 0.1 to 5 KOHmg / g. When the hydroxyl value is lower than 0.1 KOHmg / g, the bonding property between the inorganic powder and the binder is weakened, and the inorganic powder and the binder are aggregated, resulting in uneven distribution of the molten component. When the laminated CG5 is heated, a portion where the second CG4 is not softened occurs, delamination occurs, and dimensional variation increases. When the hydroxyl value of the binder exceeds 5 KOHmg / g, the binding property between the inorganic powder and the binder becomes excessively strong, and the binder and the melted component are hardly compatible. Therefore, the molten component contained in the second CG4 is not uniformly dispersed, and the molten component contained in the second CG4 that is compatible with the binder is not uniformly dispersed, and the laminated CG5 is heated to melt the molten component. Even in a molten state, a portion where the second CG 4 is not sufficiently softened occurs. Therefore, the laminated CG5 does not change its shape following the surface shapes of the first CG3 and the conductor layer 2 of another laminated CG5 'positioned below the laminated CG5, delamination occurs, and dimensional variation increases.

  Moreover, it is preferable that the glass transition point of the binder contained in 1st CG3 is -20 thru | or 10 degreeC. If the glass transition point is lower than −20 ° C., the fluidity of the binder at room temperature becomes excessive, and adhesion between the laminated CG5 occurs. When the glass transition point is higher than 10 ° C., the shape retention of the first CG 3 is insufficient, and appearance defects such as cracks and chipping of the first CG 3 are likely to occur during handling.

  The hydroxyl value of the binder contained in the first CG3 is preferably 5 to 100 KOHmg / g. When the hydroxyl value is lower than 5 KOHmg / g, the bonding property between the inorganic powder and the binder becomes weak, and density unevenness due to uneven distribution of the inorganic powder and binder occurs in the first CG3. For this reason, when the second CG 4 is deformed by heating, unevenness occurs in the deformation of the laminated CG 5, so that high dimensional accuracy cannot be maintained, delamination due to density unevenness of the inorganic powder occurs, and dimensional variation increases. . When the hydroxyl value exceeds 100 KOH mg / g, the binding property of the binder becomes excessively strong, the binder is aggregated, and density unevenness due to uneven distribution of the inorganic powder and the binder occurs in the first CG3. Therefore, when the second CG 4 is deformed by heating, unevenness occurs in the deformation of the laminated CG 5, so that delamination occurs and dimensional variation increases.

  Next, as shown in FIG. 1 (c), the first CG 3 and the second CG 4 on which the conductor layer 2 is formed are laminated and heated at a temperature at which the molten component becomes molten and softens and deforms. A laminated CG5 including the layer 2, the first CG3, and the second CG4 is manufactured.

  Here, it is important that the heating for producing the laminated CG5 is performed at a temperature 0 to 70 ° C. higher than the melting point of the molten component. As a result, an appropriate amount of molten component diffuses from the second CG 4 to the first CG 3, the bonding strength at the interface between the second CG 4 and the first CG 3 is maintained, and the CG laminate 6 is produced. At the time of heating, the second CG 4 is sufficiently softened only by heating and is deformed following the surface shapes of the first CG 3 and the conductor layer 2 of another laminated CG 5, and is sufficiently adhesive. This is because a sufficient amount of the molten component can be held in the second CG 4.

  When the lamination is performed at a temperature lower than the melting point of the molten component, the second CG 4 is not softened. Therefore, the second CG 4 is deformed following the surface shapes of the first CG 3 and the conductor layer 2 positioned above and below the second CG 4. In some cases, a gap may be generated between the first CG 3 and the second CG 4, and the molten component does not diffuse from the second CG 4 to the first CG 3. Bonding strength at the interface of CG4 is not maintained, and peeling occurs at the interface when processing such as forming a through hole for forming a through conductor or a through hole for forming a cavity in the laminated CG5 There is a case.

  Also, if the layer is laminated at a temperature higher than the melting point of the molten component by more than 70 ° C., the amount of the molten component diffused from the second CG 4 to the first CG 3 during heating is too large. The molten component cannot be retained, and when the laminated CG5 is laminated, it cannot be deformed following the surface shape of the first CG3 or the conductor layer 2 of another laminated CG5 that is in contact with the second CG4, and delamination occurs between the ceramic layers. This is because of this. Preferably, the heating is performed at a temperature 0 to 70 ° C. higher than the melting point of the molten component, and if the heating temperature is 120 ° C. or lower, organic components such as a binder and a plasticizer in the laminated CG5 are not decomposed during heating. Delamination due to cracked gas does not occur. For this purpose, as described above, a melting component having a melting point of 35 to 100 ° C. may be used. Here, the heating time when the laminated CG5 is manufactured includes the heating temperature, the type and amount of raw materials contained in the CG such as the inorganic raw materials, binders, and molten components of the first CG3 and the second CG4, the first CG3 and It depends on the CG characteristics such as the thickness of the second CG4, the lamination conditions such as the laminating apparatus and the heating method, and the bonding strength of the interface between the second CG4 and the first CG3 is maintained by the diffusion of the molten component, and the CG lamination It is adjusted so that the second CG 4 is softened and deformed during heating when the body 6 is produced and has adhesiveness. In the case of the above-described melting component and heating temperature, the heating time may be about 0.1 second to 10 minutes.

  Furthermore, when the first CG 3 and the second CG 4 are stacked and heated to produce the stacked CG 5, the second CG 4 is preferably heated at a temperature 10 to 60 ° C. higher than the melting point of the molten component. Even when the lamination conditions such as the sheet thickness or lamination time of the first CG3 fluctuate, an appropriate amount of molten component diffuses from the second CG4 to the first CG3, and the laminated CG5 is heated for a while after lamination. Even if it is left as it is, a sufficient amount of the molten component can be held in the second CG 4.

  At this time, as shown in FIG. 1B, when the second CG 4 having a small thickness is held on the support 1 ′, the first CG 3 is laminated, and the second CG 4 is broken or chipped. Is more preferable in terms of ease of handling. Further, at this time, the softened second CG 4 is pressed so as to assist in deforming following the surface shape of the first CG 3 so that the stacked stacked CGs 5 are not displaced. When 0.1 to 1 MPa is performed, more accurate and reliable crimping can be performed.

  Note that through conductors such as via-hole conductors and through-hole conductors for connecting the conductor layers 2 between the upper and lower layers may be formed as necessary. These through conductors are formed by means such as embedding a conductive paste in a through hole formed in the laminated CG 5 by punching, laser processing, or the like by printing or press filling. When the laminated CG5 is thick, the through-hole processing is preferable because punching has no difference in the through-hole diameters on the front and back of the laminated CG5. Moreover, when processing a through-hole, you may peel and laminate | stack CG5 from the support body 1, but when it hold | maintains on the support body 1, since deformation | transformation of the lamination | stacking CG5 can be prevented, it is more preferable.

  When an electronic component having a cavity is manufactured, a cavity-shaped through hole is formed in a part of the laminated CG 5 by punching with a mold or the like before the next step of producing the CG laminated body 6. The through hole may be formed before or after the conductor layer 2 is formed depending on whether or not the conductor layer 2 is formed on the inner wall surface of the cavity.

  Next, as shown in FIG. 1 (d), the laminated CG5, which is aligned and stacked, is heated at a temperature at which the molten component becomes molten and the second CG 4 is softened and deformed, that is, at a temperature about the melting point of the molten component. The CG laminated body 6 is produced by heating. Here, at the time of lamination, the laminated CG 5 can be peeled off from the support 1, and at this time, treatment such as heating can be performed as necessary. At this time, pressurization is performed so that the laminated CG5 is not displaced, and the softened second CG4 is pressed against the first CG3 and the conductor layer 2 embedded therein. And more accurate and reliable crimping becomes possible. At this time, in order to improve the adhesiveness between the laminated CGs 5, an adhesive obtained by mixing a solvent with a binder, a plasticizer, or the like may be used.

  In the process of manufacturing the CG laminate 6, the second CG 4 contains a melting component that melts when heated, so that the second CG 4 softens when the laminated CG 5 embedded with the conductor layer 2 is laminated and heated. Therefore, the second CG 4 is deformed following the surface shape formed by the first CG 3 of the laminated CG 5 positioned below the second CG 4 and the conductor layer 2 embedded therein. As a result, the laminated CGs 5 are in close contact with each other without generating a gap around the conductor layer 2 or between the conductor layers 2, and delamination does not occur in the electronic component obtained by firing the CG laminate 6.

  In addition, since the second CG 4 contains a melting component that melts when heated, the second CG 4 is softened and has adhesiveness only by heating, so there is no need to press the laminated CG 5 with a large applied pressure. Since the first CG 3 formed by embedding the conductor layer 2 does not contain a melting component that melts when heated, the first CG 3 is not deformed when heated, and the stacked laminated CGs 5 are misaligned. In addition, the second CG 4 that has been softened is not deformed to the extent that it is pressed against the first CG 3 and the conductor layer 2 that is embedded and formed therein. Therefore, the shape of the laminated CG 5 and the conductor layer 2 embedded in the laminated CG 5 is not deformed, and further obtained by firing the CG laminated body 6 obtained without distortion to the laminated CG 5 due to pressurization. The obtained electronic component has high dimensional accuracy.

  In addition, when the heating temperature at the time of producing the CG laminated body 6 is 120 ° C. or less, organic components such as a binder and a plasticizer in the laminated CG 5 are not decomposed and no decomposition gas is generated. It becomes possible to produce a few laminated bodies.

  For example, when the laminated CG layer 5 that does not contain a melting component that melts upon heating is used, the dimensional accuracy of the CG laminate 6 and the electronic component was about ± 0.5% (dimensional error). When the laminated CG5 containing the components is used, it has been experimentally found that the dimensional accuracy of the CG laminated body 6 and the electronic component is about ± 0.2%, which is greatly improved.

  In addition, when manufacturing an electronic component having a cavity, it is not necessary to press the laminated CG5 with a large pressure, so that the warping of the cavity bottom due to the difference in the elongation of the laminated CG5 due to the pressurization between the cavity periphery and the cavity bottom occurs. Thus, an electronic component can be obtained in which an electronic element can be mounted accurately and reliably on the bottom of the cavity.

  As the stack CG5 positioned at the lowermost part of FIG. 1D, a stack CG5 'composed of only the first CG3 may be used. In the case of an electronic component in which the conductor layer 2 is not exposed on the surface, such as a multilayer capacitor, a multilayer CG5 in which the conductor layer 2 is not formed may be used as the multilayer CG5 positioned at the top of FIG. In the case of an electronic component in which the conductor layer 2 is exposed on both surfaces, such as a wiring board, a device in which the conductor layer 5 is formed on both surfaces of the lowermost CG 5 ′ may be used.

  On the second CG 4 containing the molten component formed on the support 1, the first CG 3 not containing the molten component is formed to form a laminated CG 5, and a conductor is formed on the first CG 3 of the laminated CG 5. After the layer 2 is formed, delamination can be prevented and an electronic component that is not deformed by the lamination pressure can be manufactured even by a method in which a plurality of laminated CGs 5 on which the conductor layer 2 is formed are heated. In this method, since the thickness of the second CG 4 containing the molten component is required to be greater than the thickness of the conductor layer 2, when the thickness of the laminated CG 5 is thin, the second CG 4 containing the molten component, that is, deformed by heating. The proportion of the thickness of CG4 increases, and the entire laminated CG5 is easily deformed. On the other hand, in the manufacturing method of the present invention, the surface of the laminated CG 5 on which the conductor layer 2 is formed is a substantially flat surface, and thus the thickness of the second CG 4 that deforms following the shape of this surface. Can be made thinner. Therefore, even when the thickness of the laminated CG5 is thin, it is more preferable because deformation of the laminated CG5 due to heating during lamination can be suppressed and high dimensional accuracy can be ensured.

  Finally, the electronic component of the present invention is manufactured by firing the CG laminate 6. The firing process consists of removing organic components and sintering ceramic powder. The organic component is removed by heating the CG laminate 6 in a temperature range of 100 to 800 ° C., the organic component is decomposed and volatilized, and the sintering temperature varies depending on the ceramic composition, and is within a range of about 800 to 1600 ° C. Do. The firing atmosphere varies depending on the ceramic powder and the conductor material, and is performed in the air, in a reducing atmosphere, in a non-oxidizing atmosphere or the like, and may contain water vapor or the like in order to effectively remove organic components.

  The electronic component after firing is exposed to the surface of the conductor layer 2 exposed on the surface thereof for preventing corrosion of the conductor layer 2 or having good connection means for connecting to an external substrate such as solder or metal wire or an electronic component. Therefore, Ni or Au plating may be applied.

When a low-temperature sintered material such as glass ceramics is used as the ceramic material, if a constrained green sheet is further laminated on the upper and lower surfaces of the CG laminate 6 and fired, and the restraint sheet is removed after firing, higher dimensions are obtained. An accurate ceramic substrate can be obtained. The constrained green sheet is a green sheet mainly composed of a hardly sinterable inorganic material such as Al ₂ O ₃ and does not shrink during firing. In the laminate in which the constrained green sheets are laminated, shrinkage in the laminating plane direction (xy plane direction) is suppressed by the constraining green sheet that does not shrink, and shrinks only in the laminating direction (z direction). Is suppressed. If the constraining green sheet at this time also has the first CG3 and the second CG4 similar to the laminated CG5 of the present invention, a large pressing force is not required even when the constraining green sheets are laminated and pressure-bonded. The obtained electronic component may be of higher dimensional accuracy.

  Further, when such a constrained firing method is used, the constrained green sheet suppresses shrinkage in the direction of the lamination plane, so that it becomes easier to use a metal foil or a metal film that does not shrink during firing as the conductor layer 2. . The conductor layer 2 formed of a metal foil or a metal film has a lower conductor resistance and less variation in shape compared to the conductor layer 2 formed by a printing method. It is more preferable because the electrical characteristics such as the stability of the resistance and the like, and the high frequency characteristics can be improved by reducing the loss of the signal when the high frequency signal is transmitted.

  In addition to the hardly sinterable inorganic component, the constrained green sheet may contain a glass component having a softening point equal to or lower than the firing temperature, for example, the same glass as the glass in the laminated CG5. This is because the glass softens during bonding and is bonded to the laminated CG5, whereby the bonding between the laminated CG5 and the constraining green sheet is strengthened and a more reliable restraining force can be obtained. When the glass amount at this time is 0.5 to 15% by mass with respect to the inorganic component including the hardly sinterable inorganic component and the glass component, the binding force is improved and the firing shrinkage of the constraint green sheet is 0.5%. It is suppressed to the following.

  After firing, the constraining sheet is removed. Examples of the removal method include polishing, water jet, chemical blasting, sand blasting, wet blasting (a method of spraying abrasive grains and water by air pressure) and the like.

  The electronic component manufactured by the method as described above does not have delamination inside and has high dimensional accuracy, and thus has excellent electrical characteristics and high airtightness required as an electronic component.

  First, a conductive layer was formed on a PET film as a support by printing a predetermined pattern with a thickness of 10 to 20 μm by a screen printing method using a conductive paste mainly composed of tungsten.

  Next, for the first CG, 90 parts by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a coloring pigment are combined. To 100 parts by mass of ceramic powder prepared at a rate of 10 parts by mass, 10 parts by mass of a methyl methacrylate resin as a binder and 10 parts by mass of dibutyl phthalate as a plasticizer are added outside, and toluene and ethyl acetate are added. A first CG ceramic slurry was prepared by mixing with a ball mill as a solvent, applied to a PET film having a conductor layer with a thickness of 100 μm by a lip coater method, and dried to produce a first CG. .

  Next, for the second CG, 90 parts by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a coloring pigment are combined. With respect to 100 parts by mass of ceramic powder prepared at a ratio of 10 parts by mass, 18, 19, 20, 23, 25, 26, and 30 parts by mass of methyl methacrylate resin are respectively added and prepared as a melting point. A ceramic slurry was prepared by mixing 10 parts by mass of hexadecanol as a molten component having a temperature of 35 to 100 ° C. by a ball mill using toluene and ethyl acetate as solvents. Using this ceramic slurry, a second CG was prepared by applying a 50 μm thickness on a PET film by a lip coater method and drying.

  By laminating these first CG and second CG at 40 ° C. and 0.5 MPa and heating, a laminated CG composed of the conductor layer and the first and second CGs was formed.

  Four laminated CGs each having a conductor layer were superposed and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce a CG laminate. The peel strength at that time was determined as a non-defective product when the peel-off occurrence location when the CG laminate was peeled was observed with a binocular microscope, and the peel-off location was in the first CG.

Then, in order to remove organic components such as a binder in the obtained CG laminate and carbon remaining after the organic components were decomposed, about 1000 ° C. in a nitrogen atmosphere containing water vapor of 7.33 × 10 ³ Pa. After performing heat treatment for 1 hour at a temperature of 1, a sintered body (ceramics) for evaluation was produced by holding for 1 hour at a temperature of about 1600 ° C. in a reducing atmosphere. The cross section (cross section) of this sintered body was observed, and the delamination between ceramic layers, the presence or absence of bumps and pinholes, and the product dimensions were investigated. Table 1 shows the evaluation results for each binder amount of the second CG.

In Table 1, "O" in the peel strength column indicates that the peeled portion was in the first CG when the CG laminate was peeled. “Δ” indicates that it was outside the first CG. Further, “◯” in the column of the lamination dimension indicates that the dimension after lamination was measured with a three-dimensional measuring machine, and the dimensional variation was smaller than ± 0.05%. “Δ” indicates that although there was no problem in the product dimensions, the dimensional variation was ± 0.05% or more. In addition, “◯” in the column of the presence / absence of inner layer delamination indicates that no delamination was observed inside the sintered body, which was excellent. “Δ” indicates that although there was no problem in forming the CG laminate, delamination was observed inside the sintered body. In addition, “◯” in the column of presence / absence of buku / pinhole indicates that there is no buku or pinhole inside the sintered body. “Δ” indicates that there was no problem in the formation of the CG laminate, but burr and pinholes were observed inside the sintered body.

  From Table 1, sample No. with the addition amount of the binder contained in 2nd CG being less than 19 mass parts is shown. In No. 1, the peeled portion was outside the first CG, and delamination occurred inside the sintered body.

  In addition, Sample No. with the addition amount larger than 25 parts by mass. Nos. 6 and 7 had a stacking size variation of ± 0.05% or more, delamination was observed inside the sintered body, and burr / pinholes were observed.

  On the other hand, sample No. with the above addition amount of 19 to 25 parts by mass. Nos. 2, 3, 4, and 5 are peeled off in the first CG, the variation in the stacking dimension is less than ± 0.05%, there is no delamination inside the sintered body, and the bokeh / pinhole is also seen. I couldn't.

  In the same manner as in Example 1, a conductor layer was formed on a PET film as a support by printing a predetermined pattern with a thickness of 10 to 20 μm by a screen printing method using a conductor paste mainly composed of tungsten.

  Next, for the first CG, 90 parts by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a coloring pigment are combined. To 100 parts by mass of ceramic powder prepared at a rate of 10 parts by mass, 10 parts by mass of a methyl methacrylate resin as a binder and 10 parts by mass of dibutyl phthalate as a plasticizer are added outside, and toluene and ethyl acetate are added. A first CG ceramic slurry is prepared by mixing with a ball mill as a solvent, applied to the PET film on which the conductor layer is formed at a thickness of 100 μm by the lip coater method, and dried to produce the first CG. did.

  Next, for the second CG, 90 parts by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a coloring pigment are combined. 20 parts by mass of methyl methacrylate resin in solid content and 40,80,000, 100,000, 200,000, 300,000 molecular weight of methyl methacrylate resin with respect to 100 parts by mass of ceramic powder prepared at a ratio of 10 parts by mass , 360,000 and 500,000, respectively, and prepared by mixing 10 parts by mass of hexadecanol as a melting component having a melting point of 35 to 100 ° C. with a solid content, toluene and ethyl acetate as solvents, and mixing for 40 hours. A ceramic slurry was prepared. Using this ceramic slurry, it was applied to a PET film with a thickness of 50 μm by the lip coater method and dried to form a second CG. Using this second CG, five sheets were stacked and allowed to stand at room temperature for 24 hours to evaluate whether or not the second CGs adhered to each other.

  By laminating these first CG and second CG at 40 ° C. and 0.5 MPa and heating, a laminated CG composed of the conductor layer and the first and second CGs was formed.

  Four laminated CGs each having a conductor layer were superposed and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce a CG laminate. The peel strength at that time was determined as a non-defective product when the peel-off occurrence location when the CG laminate was peeled was observed with a binocular microscope, and the peel-off location was in the first CG.

Then, in order to remove organic components such as a binder in the obtained CG laminate and carbon remaining after the organic components were decomposed, about 1000 ° C. in a nitrogen atmosphere containing water vapor of 7.33 × 10 ³ Pa. After performing heat treatment for 1 hour at a temperature of 1, a sintered body for evaluation was produced by holding for 1 hour at a temperature of about 1600 ° C. in a reducing atmosphere. The cross section of the sintered body was observed, and the presence or absence of delamination between the ceramic layers and the occurrence of bumps or pinholes and the product dimensions were investigated. Table 2 shows the evaluation results by molecular weight of the second CG binder.

In Table 2, in the column of the shape retention property of the second CG, “◯” indicates that after forming the second CG, even if the five CGs are stacked and allowed to stand at room temperature for 24 hours, It shows that shape retention was maintained without sticking. “△” indicates that the second CG was molded, but when the second CG was stacked after molding and left at room temperature for 24 hours, the second CGs adhered to each other, and the shape retention could be maintained. Indicates no. In addition, “O” in the peel strength column indicates that the peeled portion was in the first CG when the CG laminate was peeled off. “Δ” indicates that it was outside the first CG. Further, “◯” in the column of the lamination dimension indicates that the dimension after lamination was measured with a three-dimensional measuring machine, and the dimensional variation was smaller than ± 0.05%. “Δ” indicates that although there was no problem in the product dimensions, the dimensional variation was ± 0.05% or more. In addition, “◯” in the column of the presence / absence of inner layer delamination indicates that no delamination was observed inside the sintered body, which was excellent. “Δ” indicates that although there was no problem in the formation of the laminate, delamination was observed inside the sintered body. In addition, “◯” in the column of presence / absence of buku / pinhole indicates that there is no buku or pinhole inside the sintered body. “Δ” indicates that there was no problem in the formation of the CG laminate, but burr and pinholes were observed inside the sintered body.

  From Table 2, the sample No. with the molecular weight of the binder contained in the second CG being less than 80,000 is shown. In No. 1, the shape retention of the second CG could not be maintained, the dimensional variation of the lamination dimension was 0.05% or more, delamination occurred inside the sintered body, and burr / pinholes were observed.

  In addition, the sample No. In Nos. 6 and 7, the peeled portion was outside the first CG, the dimensional variation of the stacking dimension was 0.05% or more, delamination occurred inside the sintered body, and bokeh / pinholes were observed.

  On the other hand, sample Nos. With a molecular weight of 80,000 to 300,000 are used. 2, 3, 4, and 5, the shape retention of the second CG is obtained, the peeled portion is within the first CG, and the dimensional variation of the lamination dimension is less than ± 0.05%, and the inside of the sintered body There was no delamination and no buku / pinholes were seen. There was no inner layer delamination and the dimensional variation was excellent.

  In the same manner as in Example 2, first, a conductive layer was formed by printing a predetermined pattern with a thickness of 10 to 20 μm on a PET film as a support by a screen printing method using a conductive paste mainly composed of tungsten. .

  Next, for the first CG, 90 parts by mass of alumina powder and alumina having an average particle diameter of 1 μm as a binder, silica, magnesia and calcia as sintering aids, and transition metal oxides as chromium pigments (chromium trioxide) ) And 10 parts by mass of ceramic powder prepared at a ratio of 10 parts by mass, 10 parts by mass of a methyl methacrylate resin as a solid content as a binder and 1 part by mass of dibutyl phthalate as a plasticizer are added. First, a ceramic slurry for CG is prepared by mixing with toluene and ethyl acetate as a solvent by a ball mill. The first CG ceramic slurry is applied on the PET film on which the conductor layer has been formed to a thickness of 100 μm by the lip coater method, and dried. 1 CG was produced.

  Next, for the second CG, 90 parts by mass of alumina powder and alumina having an average particle diameter of 1 μm as a binder, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a color pigment ) And 100 parts by mass of the ceramic powder prepared at a ratio of 10 parts by mass, the methyl methacrylate resin is 20 parts by mass in solid content, and the acid value of the methyl methacrylate resin binder is 0.0, 0.0. 1 and 0.5, 0.8, 0.9, and 1.5, respectively. As a melting component having a melting point of 35 to 100 ° C., 10 parts by mass of hexadecanol as a melting component, toluene and A ceramic slurry was prepared by mixing for 40 hours with a ball mill using ethyl acetate as a solvent. Using this ceramic slurry, it was applied to a PET film with a thickness of 50 μm by the lip coater method and dried to form a second CG.

  By laminating these first CG and second CG at 40 ° C. and 0.5 MPa and heating, a laminated CG composed of the conductor layer and the first and second CGs was formed.

  Four laminated CGs each having a conductor layer were superposed and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce a CG laminate. The peel strength at that time was determined as a non-defective product when the peel-off occurrence location when the CG laminate was peeled was observed with a binocular microscope, and the peel-off location was in the first CG.

Then, in order to remove organic components such as a binder in the obtained CG laminate and carbon remaining after the organic components were decomposed, about 1000 ° C. in a nitrogen atmosphere containing water vapor of 7.33 × 10 ³ Pa. After performing heat treatment for 1 hour at a temperature of 1, a sintered body for evaluation was produced by holding for 1 hour at a temperature of about 1600 ° C. in a reducing atmosphere. The cross section of the sintered body was observed, and the presence or absence of delamination between the ceramic layers and the occurrence of bumps or pinholes and the product dimensions were investigated. Table 3 shows the evaluation results by acid value of the second CG binder.

In Table 3, “O” in the peel strength column indicates that the peeled portion was in the first CG when the CG laminate was peeled off. “Δ” indicates that it was outside the first CG. The column “◯” in the presence / absence of inner layer delamination indicates that no delamination was observed inside the sintered body, which was excellent. “Δ” indicates that although there was no problem in the formation of the laminate, delamination was observed inside the sintered body. Further, “◯” in the column of the lamination dimension indicates that the dimension after lamination was measured with a three-dimensional measuring machine, and the dimensional variation was smaller than ± 0.05%. “Δ” indicates that although there was no problem in the product dimensions, the dimensional variation was ± 0.05% or more.

  From Table 3, sample No. whose acid value of the binder contained in 2nd CG is less than 0.1 KOHmg / g. In No. 1, the peeled portion was outside the first CG, the dimensional variation of the lamination dimension was ± 0.05% or more, and delamination occurred inside the sintered body.

  In addition, sample No. whose acid value is larger than 0.8 KOHmg / g. In Nos. 5 and 6, the peeled portion was outside the first CG, the dimensional variation of the lamination dimension was ± 0.05% or more, and delamination occurred inside the sintered body.

  On the other hand, sample No. 1 in which the added amount of the binder contained in the second CG is 0.1 to 0.8 parts by mass. In Nos. 2, 3 and 4, the peeled portion was in the first CG, the dimensional variation of the lamination dimension was less than ± 0.05%, and there was no delamination inside the sintered body.

  In the same manner as in Example 3, first, a conductive layer was formed by printing a predetermined pattern with a thickness of 10 to 20 μm on a PET film as a support by a screen printing method using a conductive paste mainly composed of tungsten. .

  Next, for the first CG, 90 parts by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a coloring pigment are combined. 6,8,10,12,15,18,20,22,24 parts by weight of methyl methacrylate resin as a binder is added to 100 parts by weight of ceramic powder prepared at a ratio of 10 parts by weight. Then, 1 part by weight of dibutyl phthalate as a plasticizer was added and prepared, mixed with a ball mill using toluene and ethyl acetate as a solvent to prepare a first CG ceramic slurry, and the above-mentioned PET having the conductor layer formed thereon A first CG was prepared by applying the film on the film by a lip coater method at a thickness of 100 μm and drying.

  Next, for the second CG, 90 parts by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a coloring pigment are combined. Hexadecanol as a melting component having a melting point of 35 to 100 ° C. is prepared by adding 20 parts by mass of methyl methacrylate resin as a solid content to 100 parts by mass of ceramic powder prepared at a ratio of 10 parts by mass. Was mixed by a ball mill for 40 hours using 10 parts by mass of solid, toluene and ethyl acetate as a solvent to prepare a ceramic slurry.

  Next, this ceramic slurry was applied to a PET film with a thickness of 50 μm by the lip coater method and dried to form a second CG.

  By laminating these first CG and second CG at 40 ° C. and 0.5 MPa and heating, a laminated CG composed of the conductor layer and the first and second CGs was formed.

  Four laminated CGs each having a conductor layer were stacked and heat-pressed in the thickness direction at a pressure of 0.5 MPa and a temperature of 80 ° C. to produce a CG laminate.

Then, in order to remove organic components such as a binder in the obtained CG laminate and carbon remaining after the organic components were decomposed, about 1000 ° C. in a nitrogen atmosphere containing water vapor of 7.33 × 10 ³ Pa. After performing heat treatment for 1 hour at a temperature of 1, a sintered body for evaluation was produced by holding for 1 hour at a temperature of about 1600 ° C. in a reducing atmosphere. The cross section of this sintered body was observed, and the delamination between the ceramic layers was investigated. Table 4 shows the results of evaluation according to the addition amount of the binder contained in the first CG.

“◯” in the column of presence / absence of inner layer delamination in Table 4 indicates that no delamination was observed inside the sintered body, which was excellent. “Δ” indicates that although there was no problem in forming the CG laminate, delamination was observed inside the sintered body.

  From Table 4, sample No. in which the addition amount of the binder contained in the first CG is less than 8 parts by mass. In No. 1, delamination occurred inside the sintered body.

  In addition, sample No. in which the addition amount is larger than 20 parts by mass. In 8 and 9, delamination occurred inside the sintered body.

  On the other hand, sample Nos. 8 to 20 parts by mass are added. 2, 3, 4, 5, 6, and 7 had no inner layer delamination.

  In the same manner as in Example 4, first, a conductive layer was formed by printing a predetermined pattern with a thickness of 10 to 20 μm on a PET film as a support by a screen printing method using a conductive paste mainly composed of tungsten. .

  Next, for the first CG, 90 parts by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a coloring pigment are combined. To 100 parts by mass of ceramic powder prepared at a ratio of 10 parts by mass, 10 parts by mass of a methyl methacrylate resin as a binder is added outside as a solid, and the molecular weight of this methyl methacrylate resin is 10,000, 50,000, 100,000. , 400,000, 800,000, 900,000, 1 million respectively. In addition, 1 part by weight of dibutyl phthalate was added as a plasticizer, and toluene and ethyl acetate were mixed by a ball mill using a solvent as a solvent to prepare a first CG ceramic slurry. The first CG was prepared by applying the film by a lip coater method at a thickness of 100 μm and drying.

  Next, for the second CG, 90 parts by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a coloring pigment are combined. To 100 parts by mass of the ceramic powder prepared at a rate of 10 parts by mass, 20 parts by mass of methyl methacrylate resin was added externally and prepared, and hexadecanol was added as a melting component having a melting point of 35 to 100 ° C. 10 parts by mass in solid content, toluene and ethyl acetate as solvent, mixed for 40 hours by ball mill to prepare a ceramic slurry, coated on PET film with a thickness of 50 μm by the lip coater method, and dried to give the second CG Formed.

  By laminating these first CG and second CG at 40 ° C. and 0.5 MPa and heating, a laminated CG composed of the conductor layer and the first and second CGs was formed.

  Four laminated CGs each having a conductor layer were stacked and heat-pressed in the thickness direction at a pressure of 0.5 MPa and a temperature of 80 ° C. to produce a CG laminate. In addition, the back surface of the second CG was observed to investigate pinholes.

Then, in order to remove organic components such as a binder in the obtained CG laminate and carbon remaining after the organic components were decomposed, about 1000 ° C. in a nitrogen atmosphere containing water vapor of 7.33 × 10 ³ Pa. After performing heat treatment for 1 hour at a temperature of 1, a sintered body for evaluation was produced by holding for 1 hour at a temperature of about 1600 ° C. in a reducing atmosphere. The cross section of the sintered body was observed, and the presence or absence of delamination between the ceramic layers and the occurrence of bumps or pinholes and the product dimensions were investigated. Table 5 shows the results of evaluation according to the molecular weight of the binder contained in the first CG.

“◯” in the column of presence / absence of inner layer delamination in Table 5 indicates that the delamination was not observed inside the sintered body and was excellent. “Δ” indicates that although there was no problem in the formation of the laminate, delamination was observed inside the sintered body. Further, “◯” in the column of the presence or absence of pinholes in the first CG layer indicates that there are no pinholes on the back surface of the first CG layer. “Δ” indicates that a pinhole was found on the back surface of the first CG layer.

  From Table 5, sample No. with a molecular weight of less than 50,000 in the binder contained in the first CG is shown. In No. 1, delamination occurred inside the sintered body.

  Sample Nos. With molecular weights greater than 800,000 were used. In 6 and 7, pinholes occurred on the back surface of the first CG.

  On the other hand, sample Nos. With a molecular weight of 50,000 to 800,000 were used. Nos. 2, 3, 4, and 5 were excellent because there was no inner layer delamination and no pinholes on the back surface of the second CG.

  In the same manner as in Example 5, first, a conductive layer was formed by printing a predetermined pattern with a thickness of 10 to 20 μm on a PET film as a support by a screen printing method using a conductive paste mainly composed of tungsten. .

  Next, for the first CG, 90 parts by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a coloring pigment are combined. To 100 parts by mass of the ceramic powder prepared at a ratio of 10 parts by mass, 10 parts by mass of a methyl methacrylate resin as a binder is added outside as a solid, and the acid value of this methyl methacrylate resin is 0.0,0.1. , 0.5, 1.0, 5.0, 8.0 KOH mg / g. Also, 1 part by weight of dibutyl phthalate was added as a plasticizer, and a ceramic slurry for the first CG was prepared by mixing with toluene and ethyl acetate as a solvent by a ball mill, on the PET film on which the conductor layer was formed. The first CG was produced by applying the lip coater at a thickness of 100 μm and drying.

  Next, for the second CG, 90 parts by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a coloring pigment are combined. To 100 parts by mass of the ceramic powder prepared at a rate of 10 parts by mass, 20 parts by mass of methyl methacrylate resin was added externally and prepared, and hexadecanol was added as a melting component having a melting point of 35 to 100 ° C. 10 parts by mass in solid content, toluene and ethyl acetate as solvent, mixed for 40 hours by ball mill to prepare a ceramic slurry, coated on PET film with a thickness of 50 μm by the lip coater method, and dried to give the second CG Formed.

  By laminating these first CG and second CG at 40 ° C. and 0.5 MPa and heating, a laminated CG composed of the conductor layer and the first and second CGs was formed.

  Four laminated CGs each having a conductor layer were superposed and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce a CG laminate. In addition, the back surface of the first CG layer was observed to investigate pinholes.

Then, in order to remove organic components such as a binder in the obtained CG laminate and carbon remaining after the organic components were decomposed, about 1000 ° C. in a nitrogen atmosphere containing water vapor of 7.33 × 10 ³ Pa. After performing heat treatment for 1 hour at a temperature of 1, a sintered body for evaluation was produced by holding for 1 hour at a temperature of about 1600 ° C. in a reducing atmosphere. The cross section of the sintered body was observed, and the delamination between the ceramic layers and the product dimensions were investigated. And the evaluation result according to the acid value of the binder contained in 1st CG is shown in Table 6.

“◯” in the column of presence / absence of inner layer delamination in Table 6 indicates that no delamination was observed inside the sintered body, which was excellent. “Δ” indicates that although there was no problem in the formation of the laminate, delamination was observed inside the sintered body. In addition, “◯” in the first CG pinhole presence / absence column indicates that there is no pinhole on the back surface of the first CG. “Δ” indicates that a pinhole was found on the back surface of the first CG layer.

  From Table 6, sample No. whose acid value of the binder contained in the first CG is less than 0.1 KOH mg / g. In No. 1, delamination occurred inside the sintered body.

  In addition, sample No. whose acid value is larger than 5.0 KOHmg / g. In No. 6, a pinhole occurred on the back surface of the first CG.

  On the other hand, Sample No. with the acid value of 0.1 to 5.0 KOHmg / g. Nos. 2 to 5 were excellent with no occurrence of delamination and pinholes.

  In the same manner as in Example 6, first, a conductive layer was formed by printing a predetermined pattern with a thickness of 10 to 20 μm on a PET film as a support by a screen printing method using a conductive paste mainly composed of tungsten. .

  Next, for the first CG, 90 parts by mass of alumina powder and alumina having an average particle diameter of 1 μm as a binder, silica, magnesia and calcia as sintering aids, and transition metal oxides as chromium pigments (chromium trioxide) ) And 10 parts by mass of ceramic powder prepared at a ratio of 10 parts by mass, 10 parts by mass of a methyl methacrylate resin as a solid content as a binder and 1 part by mass of dibutyl phthalate as a plasticizer are added. First, a ceramic slurry for CG is prepared by mixing with toluene and ethyl acetate as a solvent by a ball mill. The first CG ceramic slurry is applied on the PET film on which the conductor layer has been formed to a thickness of 100 μm by the lip coater method, and dried. 1 CG was produced.

  Next, for the second CG, 90 parts by mass of alumina powder and alumina having an average particle diameter of 1 μm as a binder, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a color pigment ) And 10 parts by mass of ceramic powder prepared at a ratio of 10 parts by mass, the methyl methacrylate resin is 20 parts by mass in solid content, and the glass transition point of the methyl methacrylate resin binder is -25, -20 , -10, -5, 0, 5, 10 ° C, respectively, and prepared by adding 10 parts by mass of hexadecanol as a melting component having a melting point of 35 to 100 ° C, and toluene and ethyl acetate as solvent. And mixing for 40 hours with a ball mill to prepare a ceramic slurry, applying it to a PET film with a thickness of 50 μm by the lip coater method, and drying to form a second CG. Formed. Using this second CG, five sheets were stacked and allowed to stand at room temperature for 24 hours to evaluate whether or not the second CGs adhered to each other.

  By laminating these first CG and second CG at 40 ° C. and 0.5 MPa and heating, a laminated CG composed of the conductor layer and the first and second CGs was formed.

  Four laminated CGs each having a conductor layer were superposed and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce a CG laminate.

Then, in order to remove organic components such as a binder in the obtained CG laminate and carbon remaining after the organic components were decomposed, about 1000 ° C. in a nitrogen atmosphere containing water vapor of 7.33 × 10 ³ Pa. After performing heat treatment for 1 hour at a temperature of 1, a sintered body for evaluation was produced by holding for 1 hour at a temperature of about 1600 ° C. in a reducing atmosphere. The cross section of the sintered body was observed, and the presence or absence of delamination between the ceramic layers and the product dimensions were investigated. And the evaluation result according to the glass transition point of the binder contained in 2nd CG is shown in Table 7.

In Table 7, “◯” in the column of the shape retention property of the second CG indicates that each of the second CGs of the second CG is formed even if the two CGs are molded and then stacked for 5 hours. It shows that shape retention was maintained without sticking. “△” indicates that the second CG was molded, but when the second CG was stacked after molding and left at room temperature for 24 hours, the second CGs adhered to each other and the shape retention was maintained. Indicates that it was not possible. Further, “◯” in the column of the lamination dimension indicates that the dimension after lamination was measured with a three-dimensional measuring machine, and the dimensional variation was smaller than ± 0.05%. “Δ” indicates that although there was no problem in the product dimensions, the dimensional variation was ± 0.05% or more. In addition, “◯” in the column of the presence or absence of inner layer delamination indicates that no delamination was observed inside the sintered body, which was excellent. “Δ” indicates that although there was no problem in the formation of the laminate, delamination was observed inside the sintered body.

  From Table 7, Sample No. whose glass transition point of the binder contained in 2nd CG is lower than -20 degreeC. For No. 1, the shape retention of the second CG could not be maintained, and the dimensional variation in the lamination dimension was 0.05% or more.

  In addition, Sample No. with a glass transition point higher than 0 ° C. was used. In Nos. 6 and 7, the peeled portion was outside the first CG layer, the dimensional variation in the lamination dimension was 0.05% or more, and delamination occurred inside the sintered body.

  On the other hand, Sample No. with a glass transition point of −20 to 0 ° C. 2-5, the shape retention of the second CG is obtained, the peeled portion is in the first CG layer, and the dimensional variation of the lamination dimension is less than ± 0.05%, and the inside of the sintered body No delamination was seen.

  In the same manner as in Example 7, first, a conductive layer was formed by printing a predetermined pattern with a thickness of 10 to 20 μm on a PET film as a support by a screen printing method using a conductive paste mainly composed of tungsten. .

  Subsequently, for the first CG, 90 parts by mass of alumina powder and an alumina having an average particle diameter of 1 μm as a binder, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a coloring pigment are used. ) And 10 parts by mass of ceramic powder prepared at a ratio of 10 parts by mass, 10 parts by mass of a methyl methacrylate resin as a solid content as a binder and 1 part by mass of dibutyl phthalate as a plasticizer are added. A ceramic slurry for the second CG is prepared by mixing with toluene and ethyl acetate as a solvent by a ball mill, applied onto the PET film on which the conductor layer is formed at a thickness of 100 μm by the lip coater method, and then dried. 1 CG was produced.

  Next, for the second CG, 90 parts by mass of alumina powder and alumina having an average particle diameter of 1 μm as a binder, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a color pigment ) And 100 parts by mass of ceramic powder prepared at a ratio of 10 parts by mass, the methyl methacrylate resin is 20 parts by mass in solid content, and the hydroxyl value of the methyl methacrylate resin binder is 0,0.1, 1,3,4,5,5.5,6KOHmg / g, each of which is added and prepared, 10 parts by mass of hexadecanol as a melting component having a melting point of 35 to 100 ° C., toluene and ethyl acetate Is mixed with a ball mill for 40 hours using a solvent as a solvent to prepare a ceramic slurry, coated on a PET film by a lip coater method at a thickness of 50 μm, and dried to form a second C G was formed.

  By laminating these first CG and second CG at 40 ° C. and 0.5 MPa and heating, a laminated CG composed of the conductor layer and the first and second CGs was formed.

  Four laminated CGs each having a conductor layer were superposed and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce a CG laminate.

Then, in order to remove organic components such as a binder in the obtained CG laminate and carbon remaining after the organic components were decomposed, about 1000 ° C. in a nitrogen atmosphere containing water vapor of 7.33 × 10 ³ Pa. After performing heat treatment for 1 hour at a temperature of 1, a sintered body for evaluation was produced by holding for 1 hour at a temperature of about 1600 ° C. in a reducing atmosphere. The cross section of the sintered body was observed, and the presence or absence of delamination between the ceramic layers and the product dimensions were investigated. Table 8 shows the evaluation results by hydroxyl value of the first CG binder.

“◯” in the column of the stacking dimension in Table 8 indicates that the dimension after stacking was measured with a three-dimensional measuring machine and the dimensional variation was smaller than ± 0.05%. “Δ” indicates that although there was no problem in the product dimensions, the dimensional variation was ± 0.05% or more. In addition, “◯” in the column of the presence or absence of inner layer delamination indicates that no delamination was observed inside the sintered body, which was excellent. “Δ” indicates that although there was no problem in the formation of the laminate, delamination was observed inside the sintered body.

  From Table 8, Sample No. with a hydroxyl value of the binder contained in the second CG of less than 0.1 KOHmg / g. In No. 1, the dimensional variation of the lamination dimension was ± 0.05% or more, and delamination occurred in the sintered body.

  In addition, Sample No. whose hydroxyl value was larger than 5 KOHmg / g. In Nos. 7 and 8, the dimensional variation of the lamination dimension was ± 0.05% or more, and delamination occurred in the sintered body.

  On the other hand, Sample No. with the hydroxyl value of 0.1 to 5 KOHmg / g. In Nos. 2 to 6, the dimensional variation in the lamination dimension was smaller than ± 0.05%, and no delamination was observed inside the sintered body.

  90 parts by mass of alumina having an average particle diameter of 1 μm for the first CG, 10 parts by mass of silica, magnesia and calcia as sintering aids, and transition metal oxide (chromium trioxide) as a coloring pigment 10 parts by mass of a methyl methacrylate resin is added as a solid content to 100 parts by mass of the ceramic powder prepared at a ratio of, and the glass transition point of this methyl methacrylate resin is −22, −20, 0, 10, 20 , Each was added externally at 25 ° C. In addition, 1 part by weight of dibutyl phthalate was added as a plasticizer, and toluene and ethyl acetate were mixed in a ball mill for 40 hours using a solvent to prepare a slurry. Using a die coater sheet molding machine, a molding speed of 2 m / min was obtained. The first CG was prepared by applying the first CG with a thickness of 100 μm under a condition where the width of the molded sheet was 250 mm and drying.

  Next, for the second CG, 90 parts by mass of alumina powder and alumina having an average particle diameter of 1 μm as a binder, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a color pigment ) And 100 parts by mass of the ceramic powder prepared at a ratio of 10 parts by mass, 20 parts by mass of methyl methacrylate resin in solid content, and by adding a binder of methyl methacrylate resin, the melting point is Hexadecanol as a melting component at 35 to 100 ° C. is mixed in a solid content of 10 parts by mass, toluene and ethyl acetate as a solvent are mixed for 40 hours by a ball mill to prepare a ceramic slurry, and the thickness is formed on a PET film by a lip coater method. A second CG was formed by coating at 50 μm and drying.

  By laminating these first CG and second CG at 40 ° C. and 0.5 MPa and heating, a laminated CG composed of the conductor layer and the first and second CGs was formed.

Using this laminated CG, the adhesion between the laminated CGs at the time of handling at normal temperature and the evaluation of the cracks in the laminated CGs were evaluated. Table 9 shows the evaluation results for each glass transition point of the binder contained in the first CG. “◯” in the column of sheet adhesion in Table 9 indicates that the laminated CGs do not adhere to each other when the laminated CGs are handled at room temperature. Shows that it was easy to handle. “Δ” indicates that the laminated CGs are attached to each other only by being stacked at room temperature and are difficult to handle. “◯” in the column of the sheet crack and chip indicates that the stack CG was easy to handle without cracking or chipping when handled at room temperature. “Δ” indicates that the laminated CG was cracked or chipped when handled at room temperature and was difficult to handle.

  From Table 9, sample No. whose glass transition point of the binder contained in 1st CG is less than -20 degreeC is shown. In No. 1, adhesion of the laminated CG sheet occurred.

  Sample No. with a glass transition point higher than 10 ° C. was used. In Nos. 5 and 6, sheet cracking or chipping of the laminated CG occurred.

  On the other hand, sample no. Nos. 2 to 4 were excellent because there was no sheet adhesion and no sheet cracking or chipping occurred.

  In the same manner as in Example 8, first, a conductor layer was formed by printing a predetermined pattern with a thickness of 10 to 20 μm on a PET film as a support by a screen printing method using a conductor paste mainly composed of tungsten. .

  Next, for the first CG, 90 parts by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a coloring pigment are combined. To 100 parts by mass of the ceramic powder prepared at a rate of 10 parts by mass, methyl methacrylate resin as a binder is added in an amount of 10 parts by mass as a binder, and the hydroxyl value of this methyl methacrylate resin is 0, 3, 5, 10 20, 40, 60, 80, 100, 104, 110 KOH mg / g. In addition, 1 part by weight of dibutyl phthalate was added as a plasticizer, and a ceramic slurry for the first CG was prepared by mixing with toluene and ethyl acetate as a solvent by a ball mill. The first CG was produced by applying at 100 μm and drying.

  Next, for the second CG, 90 parts by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as a sintering aid, and transition metal oxide (chromium trioxide) as a coloring pigment are combined. To 100 parts by mass of the ceramic powder prepared at a rate of 10 parts by mass, 20 parts by mass of methyl methacrylate resin was added externally and prepared, and hexadecanol was added as a melting component having a melting point of 35 to 100 ° C. 10 parts by mass in solid content, toluene and ethyl acetate as solvent, mixed for 40 hours by ball mill to prepare a ceramic slurry, coated on PET film with a thickness of 50 μm by the lip coater method, and dried to give the second CG Formed.

  By laminating these first CG and second CG at 40 ° C. and 0.5 MPa and heating, a laminated CG composed of the conductor layer and the first and second CGs was formed.

  Four laminated CGs each having a conductor layer were stacked and heat-pressed in the thickness direction at a pressure of 0.5 MPa and a temperature of 80 ° C. to produce a CG laminate.

Then, in order to remove organic components such as a binder in the obtained CG laminate and carbon remaining after the organic components were decomposed, about 1000 ° C. in a nitrogen atmosphere containing water vapor of 7.33 × 10 ³ Pa. After performing a heat treatment for 1 hour at a temperature of 1, a ceramic sintered body for evaluation was produced by holding at a temperature of about 1600 ° C. for 1 hour in a reducing atmosphere.

  The cross section of the sintered body was observed, and the presence or absence of delamination between the ceramic layers and the occurrence of bumps or pinholes and the product dimensions were investigated. Table 10 shows the result of evaluation according to the hydroxyl value of the binder contained in the first CG.

“◯” in the column of presence / absence of inner layer delamination in Table 10 indicates that no delamination was observed inside the sintered body, which was excellent. “Δ” indicates that although there was no problem in the formation of the laminate, delamination was observed inside the sintered body. Further, “◯” in the column of the lamination dimension indicates that the dimension after lamination was measured with a three-dimensional measuring machine, and the dimensional variation was ± 0.05% or less. “Δ” indicates that although there was no problem in the product dimensions, the dimensional variation was ± 0.05% or more.

  From Table 10, Sample No. whose hydroxyl value of the binder contained in the first CG is less than 5 KOHmg / g. In Nos. 1 and 2, delamination occurred in the sintered body, and the dimensional variation in the lamination dimension was 0.05% or more.

  In addition, Sample No. whose hydroxyl value is greater than 100 KOHmg / g. In Nos. 10 and 11, delamination occurred in the sintered body, and the dimensional variation in the lamination dimension was 0.05% or more.

  On the other hand, sample No. 5 having a hydroxyl value of 5 to 100 KOHmg / g. Nos. 3 to 9 had no inner layer delamination and were excellent in dimensional variation.

  First, in the same manner as in Example 10, first, a conductive layer is formed by printing a predetermined pattern with a thickness of 10 to 20 μm on a PET film as a support by a screen printing method using a conductive paste mainly composed of tungsten. did.

  Next, for the first CG, 90 parts by mass of alumina having an average particle diameter of 1 μm, 10 parts by mass of silica, magnesia, calcia as a sintering aid and chromium oxide of a transition metal oxide as a coloring pigment 10 parts by mass of solid isobutyl methacrylate resin as a binder is added to 100 parts by mass of the ceramic powder prepared at a ratio of 40% by mass using toluene and ethyl acetate as a solvent and a ball mill for 40 hours. Prepared. A first CG was produced by applying the film on the PET film on which the conductor layer had been formed to a thickness of 100 μm by the lip coater method and drying.

  For the second CG, 10 parts by mass of solid methyl methacrylate resin as a binder and 1 part by mass of dibutyl phthalate as a plasticizer are melted with respect to 100 parts by mass of the same ceramic powder as the first slurry. 10 parts by mass of each component was added, and toluene and ethyl acetate were used as solvents and mixed for 40 hours by a ball mill to prepare a second slurry. Three types of second slurries were prepared using melting components of tetradecanol having a melting point of 40 ° C, hexadecanol having a melting point of 50 ° C, and octadecanol having a melting point of 60 ° C. A second CG was formed by coating the film with a thickness of 50 μm by a lip coater method and drying.

  Next, the second CG was overlaid on the first CG, heated at a heating temperature as shown in Table 1, and pressurized at a pressure of 0.5 MPa to produce a laminated CG. The obtained laminated CG has a bonding strength at the interface between the first CG and the second CG by attaching a tape to the first CG and the second CG and pulling the tape in opposite directions. evaluated. The case where it did not peel at the interface but broke in the first CG or the second CG was regarded as a good product.

  Next, four laminated CGSs each having a conductor layer were stacked and thermocompression bonded in the thickness direction at a pressure of 0.5 MPa and a temperature of 80 ° C. to produce a CG laminate. The obtained CG laminate is baked at a temperature of about 1600 ° C. for 1 hour in a reducing atmosphere after removing organic components by holding it in a nitrogen atmosphere containing water vapor at a temperature of about 1000 ° C. for 1 hour. Thus, a ceramic sintered body for evaluation was produced.

The cross section (cross section) of this sintered body was observed to evaluate the occurrence of delamination between the ceramic layers. Table 11 shows the evaluation results of the bonding strength and delamination depending on the heating temperature when producing the laminated CG with respect to the melting point of the molten component.

  “◯” in the column of the bonding strength in Table 11 indicates that the film did not peel at the interface between the first CG and the second CG, but broke within the first CG or the second CG. Further, “Δ” indicates that the film was easily peeled off at the interface between the first CG and the second CG. In addition, “◯” in the column of delamination indicates that no delamination was observed in the ceramic layer of the sintered body or the periphery of the wiring conductor. “Δ” indicates that delamination was observed between the ceramic layers and around the wiring conductor.

  From Table 11, when the laminated CG was produced at a heating temperature lower than the melting point of the molten component, it was easily peeled off at the interface between the first CG and the second CG and easily peeled off after handling the laminated CG. .

  Further, when the laminated CG was produced at a heating temperature higher than 70 ° C. higher than the melting point of each molten component, delamination occurred in the ceramic layers of the sintered body and around the wiring conductor.

  On the other hand, when laminated by heating at a temperature 0 to 70 ° C. higher than the melting point of the molten component, the bonding strength between the first CG and the second CG is sufficiently higher than the strength of the first and second CG. And excellent without delamination between the ceramic layers.

  Note that the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the scope of the present invention. For example, in the example of the above-described embodiment, an inorganic powder, a binder, and a solvent are added and mixed to produce a ceramic slurry. However, a plasticizer may be added to impart flexibility to the CG, and the inorganic powder A dispersant may be added to improve the dispersibility.

(A)-(d) is sectional drawing for every process which shows an example of embodiment of the manufacturing method of the electronic component of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Support body 2 ... Conductor layer 3 ... 1st ceramic green sheet 4 ... 2nd ceramic green sheet 5 ... Laminated ceramic green sheet 6 ... Ceramic green sheet laminated body

Claims (13)

Forming a conductor layer on the support, producing a first ceramic green sheet on the support on which the conductor layer is formed, producing a second ceramic green sheet, and the first Forming a multilayer ceramic green sheet comprising the conductor layer and the first and second ceramic green sheets by laminating and heating the ceramic green sheet and the second ceramic green sheet; and the multilayer ceramic green A step of producing a ceramic green sheet laminate by laminating a plurality of sheets and heating; and a step of firing the ceramic green sheet laminate, wherein the second ceramic green sheet comprises the laminate When producing ceramic green sheets and the ceramic green sheet product Method of manufacturing an electronic component, characterized by containing the molten component as a molten state when heated at the time of making the body. The method for manufacturing an electronic component according to claim 1, wherein the melting component has a melting point of 35 to 100 ° C. 3. The method of manufacturing an electronic component according to claim 1, wherein an addition amount of the organic binder contained in the second ceramic green sheet is 19 to 25 parts by mass with respect to 100 parts by mass of the inorganic powder. . 4. The method of manufacturing an electronic component according to claim 1, wherein the organic binder contained in the second ceramic green sheet has a molecular weight of 80,000 to 300,000. 5. 5. The method of manufacturing an electronic component according to claim 1, wherein the acid value of the organic binder contained in the second ceramic green sheet is 0.1 to 0.8 KOH mg / g. 6. . 6. The electron according to claim 1, wherein an addition amount of the organic binder contained in the first ceramic green sheet is 8 to 20 parts by mass with respect to 100 parts by mass of the inorganic powder. A manufacturing method for parts. The method for producing an electronic component according to any one of claims 1 to 6, wherein the average molecular weight of the organic binder contained in the first ceramic green sheet is 50,000 to 800,000. 8. The method of manufacturing an electronic component according to claim 1, wherein the acid value of the organic binder contained in the first ceramic green sheet is 0.1 to 5 KOH mg / g. 9. The method of manufacturing an electronic component according to claim 1, wherein the glass transition point of the organic binder contained in the second ceramic green sheet is −20 to 0 ° C. 9. 10. The method of manufacturing an electronic component according to claim 1, wherein the organic binder contained in the second ceramic green sheet has a hydroxyl value of 0.1 to 5 KOH mg / g. 11. The method of manufacturing an electronic component according to claim 1, wherein the glass transition point of the organic binder contained in the first ceramic green sheet is −20 to 10 ° C. 11. The method for producing an electronic component according to any one of claims 1 to 11, wherein the organic binder contained in the first ceramic green sheet has a hydroxyl value of 5 to 100 KOHmg / g. The manufacturing of the electronic component according to any one of claims 1 to 12, wherein the heating in the step of manufacturing the multilayer ceramic green sheet is performed at a temperature 0 to 70 ° C higher than a melting point of the molten component. Method.

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