JP2006066627A - Method of manufacturing electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing electronic components with high dimensional accuracy without causing de-lamination. <P>SOLUTION: The manufacturing method includes the steps of forming a conductor layer 2 on a support 1; forming a lamination ceramic green sheet comprising the conductor layer 2 and first and second ceramic green sheet layers, by coating first ceramic slurry 3 onto the support 1 formed with the conductor layer 2, and coating and drying second ceramic slurry 4 onto the coated first ceramic slurry 3; producing a ceramic green sheet laminate 6 by laminating a plurality of the lamination ceramic green sheets 5 and heating the laminated sheets 5; and sintering the ceramic green sheet laminate 6. The second ceramic slurry 3 contains a molten component brought into a molten state in the case of heating the second ceramic slurry 3 for producing the ceramic green sheet laminate 6, and a difference between the solubility parameter of the first ceramic slurry 3 and the solubility parameter of the second ceramic slurry 4 is two or over. <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 a multilayered structure of thinner dielectric layers and conductor layers for miniaturization and higher capacity. In addition, in multilayer ceramic wiring boards, thinner insulation layers and wiring conductor layers are formed in multiple layers, and the width and spacing of the wiring conductor layers must be finer in order to reduce the size and increase the density of wiring conductors. It has been.

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

  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, a sufficient pressing force is applied to the portion where the regions where the conductor layers are formed overlap, but it is difficult to sufficiently apply the pressing force to the other portions. It tends to be sufficient pressure bonding. 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.

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

  For such a problem, Patent Document 1 proposes to use a laminate having a high fluidity 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.

  Patent Document 2 proposes that a ceramic layer containing 78% by volume or more of binder with respect to the ceramic powder is provided on at least one surface of the green sheet, and an internal conductor layer is formed on the upper surface. In the ceramic layer containing many binders, the binder flows sufficiently and delamination during firing is eliminated.

  Thus, the occurrence of delamination has been eliminated by forming a high fluidity layer in the laminate or by laminating a green sheet having a high fluidity layer formed on a normal green sheet.

  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 response to this problem, Patent Document 3 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 this 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 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 4, a ceramic sheet is coated on a support having a conductor 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 61-229551 A JP-A-5-217448 Japanese Patent Laid-Open No. 50-64768

  However, the conventional method of forming a high fluidity layer is a method of laminating a high fluidity green sheet with an increased amount of binder or plasticizer on a normal green sheet (Method A), and a method of high fluidity after drying. Since it was a method (Method B) of applying and drying a ceramic slurry (hereinafter also referred to as a slurry) to form a ceramic layer on a normal green sheet, there were the following problems.

  In Method A, a process of forming a high fluidity green sheet, a step of drilling a high fluidity green sheet, and a step of laminating a high fluidity green sheet are added to the case where only a normal green sheet is used. As a result, there are problems such as an increase in the number of steps and the number of layers, an increase in construction period, an increase in cost, a decrease in yield, and a decrease in reliability of conductor connection between layers. In addition, since the high-fluidity green sheet is thin and contains a large amount of binder and plasticizer, it is highly tacky and easily deforms.Therefore, handling is not easy, and it is difficult to escape even if air is involved during lamination. There was a problem that it was likely to cause delamination.

  In Method B, although there is no increase in the number of laminated layers, a step of applying and drying a slurry that forms a high-fluidity ceramic layer after drying after forming an ordinary green sheet is the same as described above. There were problems such as longer construction period, higher cost, and lower yield. If the solvent in the slurry is not fully studied, the lower normal green sheet is dissolved by the solvent in the slurry, or the close contact between the high fluidity layer and the lower green sheet becomes insufficient. There was a problem of generating voids.

  Further, in the conventional method using a laminate having a high fluidity portion, it is necessary to apply a high pressure of 180 MPa in the thickness direction, for example, in order to perform pressure bonding so that the high fluidity portion is moved and delamination does not occur. is there. 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 layer pattern is deformed. As a result, it is difficult to mount components on the board because the desired dimensional accuracy of the board cannot be obtained, and the conductor layer pattern shape as designed cannot be obtained. There is a problem that electrical characteristics such as matching cannot be obtained. Furthermore, the problem of voids generated around the conductor layer when the interval between the conductor layer patterns is fine remains unresolved.

  Further, in the method of providing a ceramic layer containing 78% by volume or more of binder with respect to the ceramic powder on at least one surface of the green sheet, since the pressure is 2 MPa, the shape of the green sheet or conductor pattern as described above is used. There was a problem of deformation. In addition, since it is pressure-bonded at a temperature of about 30 ° C., a ceramic layer containing a binder of 78% by volume or more becomes highly sticky at room temperature and is not easy to handle, and therefore, air is easily involved during lamination, so delamination May occur.

  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 the fine conductor layer It is difficult to print in a precise alignment with a pattern, and it is difficult to print a ceramic paste between adjacent conductor layers, particularly when the distance between conductor layer patterns is fine. For this reason, a ceramic paste is also printed on the conductor layer, and through conductors for connecting the conductor layers that are stacked and arranged above and below are connected to the conductor layer by the ceramic paste printed on the conductor layer. There was a problem of disappearing.

Further, in the method of forming a flat green sheet by applying a ceramic slurry on a support having a conductor layer formed on the surface, and then drying and peeling, 50 to 300 kg / cm ² (5 to 30 MPa) in the lamination step It is necessary to apply such a high pressure. When such a high pressure is applied to the green sheet, the shape of the green sheet or the conductor layer pattern is deformed. As a result, when an electronic component is manufactured, it is difficult to mount the component on the electronic component because the desired dimensional accuracy cannot be obtained, and the conductor layer pattern shape as designed cannot be obtained. There is a problem that electrical characteristics such as impedance matching cannot be obtained in a wiring board for use.

  Further, when an electronic component having a cavity is manufactured, a green sheet laminated body is formed by laminating a green sheet having a through hole serving as a cavity and a green sheet not having a through hole serving as a bottom of the cavity. There was a problem that the bottom of the cavity 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 It is because it is 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. In addition, 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 method of manufacturing an electronic component according to the present invention includes a step of forming a conductor layer on a support, a first ceramic slurry applied to the support on which the conductor layer is formed, and the applied first ceramic slurry Applying a second ceramic slurry thereon and drying to form a laminated ceramic green sheet comprising the conductor layer and the first and second ceramic green sheet layers; and laminating a plurality of the ceramic green sheets. A step of producing a ceramic green sheet laminate by heating and a step of firing the ceramic green sheet laminate, wherein the second ceramic slurry is used to produce the ceramic green sheet laminate. Containing a melting component that becomes a molten state when heated, and a solubility parameter of the first ceramic slurry and the The difference between the solubility parameter of the second ceramic slurry, characterized in that two or more.

  In the present invention, preferably, the second ceramic slurry contains a melting component that is in a molten state when heated when the ceramic green sheet laminate is produced.

  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 slurry is 19 to 40% by mass.

  In the present invention, it is preferable that the molecular weight of the organic binder contained in the second ceramic slurry is 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 slurry 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 slurry is 10 to 20% by mass.

  In the present invention, it is preferable that the molecular weight of the organic binder contained in the first ceramic slurry is 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 slurry is 0.1 to 5.0 KOHmg / g.

  In the present invention, preferably, the glass transition point of the organic binder contained in the second ceramic slurry is −20 to −12 ° C.

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

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

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

  In the method for manufacturing an electronic component according to the present invention, a conductor layer is formed on a support, a first ceramic slurry is applied on the support on which the conductor layer is formed, and the first ceramic slurry is applied on the applied first ceramic slurry. 2 is applied and dried to form a laminated ceramic green sheet composed of a conductor layer and first and second ceramic green sheet layers. Since the first ceramic green sheet layer made of the first ceramic slurry and the second ceramic green sheet layer made of the second ceramic slurry having the above relationship can be simultaneously formed, the number of steps and the number of laminations Without causing problems such as longer construction period, higher cost, lower yield, lower reliability of conductor connection between layers It is possible to form a fluidized layer. In addition, since there is no lamination process of the high fluidity layer, there is no air entrainment during the lamination of the high fluidity layer, and the conductor layer is formed in the multilayer ceramic green sheet. Since there is no level difference and the surface is flat, it is possible to obtain a highly reliable electronic component without delamination.

  The first ceramic slurry is applied to the support on which the conductor layer is formed by separating the solubility parameter of the first ceramic slurry and the solubility parameter of the second ceramic slurry from two or more. When the second ceramic slurry is applied onto one ceramic slurry, the first and second ceramic slurries are prevented from dissolving together, so the first ceramic green sheet formed from the first ceramic slurry It is possible to prevent the layer and the second ceramic green sheet layer formed from the second ceramic slurry from mixing and becoming identical.

  According to the method for manufacturing an electronic component of the present invention, since the second ceramic slurry contains a melting component that melts when heated when the ceramic green sheet laminate is produced, the multilayer ceramic green sheet contains the melting component. A second ceramic green sheet layer containing a first ceramic green sheet layer not containing a molten component, and the second ceramic green sheet having a conductor layer formed thereon is laminated and heated. Since the green sheet layer is softened, the second ceramic green sheet layer is deformed following the surface shapes of the first ceramic green sheet layer and the conductor layer of the laminated ceramic green sheet positioned therebelow. As a result, the laminated ceramic green sheets adhere to 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. .

  In addition, since the second ceramic green sheet layer contains a melting component that melts when heated, the second ceramic green sheet layer softens and has adhesiveness only by heating. There is no need to crimp the laminated ceramic green sheet. Since the first ceramic green sheet layer does not contain a melting component that melts when heated, the first ceramic green sheet layer is not deformed when heated, and the laminated ceramic green sheets are positioned at the time of lamination. It will not be deformed by a pressure that can be pressed so as not to slip. Therefore, since the shapes of the first ceramic green sheet layer and the conductor layer are not deformed, the obtained ceramic green sheet laminate and the electronic component obtained by firing the same have no delamination and high dimensional accuracy. It will have.

  Furthermore, when manufacturing electronic parts having cavities, there is no need to press the multilayer ceramic green sheet with a large pressure, so the cavity bottom due to the difference in the elongation of the multilayer ceramic green sheet due to the pressurization between the cavity periphery and the cavity bottom. It is possible to suppress the occurrence of warping, and it is possible to obtain an electronic component capable of accurately and reliably mounting an electronic element on the bottom of the cavity.

  In the present invention, when the melting point of the melting component that is melted during heating is 35 ° C. to 100 ° C., the second ceramic green sheet layer is not softened and deformed at room temperature. Handling is facilitated, and organic components such as a binder and a plasticizer in the multilayer ceramic green sheet are not decomposed during heating, so that delamination does not occur due to the decomposition gas, which is preferable.

  When the added amount of the binder contained in the second ceramic slurry is 19 to 40% by mass, the second ceramic green sheet layer is deformed following the shape of the first ceramic green sheet layer positioned therebelow. In addition, foam-like protrusions (bumps) and pinholes on the porcelain are not generated by the decomposition gas of the binder during firing, which is preferable.

  When the molecular weight of the binder contained in the second ceramic slurry is 80,000 to 300,000, the shape retention of the second ceramic green sheet layer is maintained, and the molten component contained in the second ceramic green sheet layer is When uniformly melted by heating, the multilayer ceramic green sheet can be heated to maintain a sufficient amount of the molten component of the second ceramic green sheet layer, and there is no distortion of the multilayer ceramic green sheet due to pressurization. This is preferable because it can be pressure-bonded with a low applied pressure.

  When the acid value of the binder contained in the second ceramic slurry is 0.1 to 0.8 KOHmg / g, the molten component contained in the second ceramic green sheet layer is uniformly dispersed when melted by heating, Preferred because the laminated ceramic green sheet can be heated to maintain a sufficient amount of the molten component of the second ceramic green sheet layer and can be pressed with low pressure so as not to cause distortion to the laminated ceramic green sheet. It becomes.

  When the addition amount of the organic binder contained in the first ceramic slurry is 10 to 20% by mass, the first ceramic from the second ceramic slurry caused by the difference in density of the ceramic slurry at the time of forming the multilayer ceramic green sheet The amount of diffusion of the molten component into the rally can be reduced, and the amount of diffusion of the molten component due to the solvent component of the first ceramic slurry can be reduced, which is preferable.

  When the molecular weight of the binder contained in the first ceramic slurry is 50,000 to 800,000, dimensional variation due to raw deformation of the first ceramic green sheet during processing of the laminated ceramic green sheet is suppressed, and the raw material components are not uniform. The occurrence of poor appearance such as pinholes in the first ceramic green sheet due to such dispersion can be suppressed, which is preferable.

  When the acid value of the binder contained in the first ceramic slurry is 0.1 to 5.0 KOHmg / g, the second ceramic green is caused by insufficient bonding between the raw material and the binder when the multilayer ceramic green sheet is heated. The diffusion of the molten component from the sheet layer to the first ceramic green sheet layer can be reduced, and the occurrence of appearance defects such as pinholes in the first ceramic green sheet layer due to aggregation of inorganic raw materials can be prevented, preferable.

  When the glass transition point of the binder contained in the second ceramic slurry is −20 to −12 ° C., the second ceramic green sheet layer is easily softened due to melting of the molten component during heating. The layer can preferably follow the shape of the first ceramic green sheet layer and the conductor pattern formed thereon, which is preferable.

  When the hydroxyl value of the binder contained in the second ceramic slurry is 0.1 to 5 KOHmg / g, the molten component contained in the second ceramic green sheet layer is uniformly dispersed when melted by heating. The green sheet can be heated to maintain a sufficient amount of the molten component of the second ceramic green sheet layer, and the laminated ceramic green sheet can be pressure-bonded at such a low pressure that there is no distortion, which is preferable. .

  When the glass transition point of the binder contained in the first ceramic slurry is −20 to 20 ° C., the hard nature of the binder appears so strongly that the first ceramic green sheet layer becomes strong, and the second ceramic green is heated during heating. The first ceramic green sheet layer suppresses even the slight dimensional deformation caused by the sheet layer softening and following the shape of the first ceramic green sheet layer and the conductor layer pattern formed thereon. This is preferable.

  When the hydroxyl value of the binder contained in the first ceramic slurry is 5 to 100 KOHmg / g, solvation is formed in the ceramic slurry by attracting the charge of the hydroxyl group with the charge existing on the surface of the inorganic powder, As a result, the laminated ceramic green sheet is formed in a uniform state, so that the inorganic powder and binder contained in the first ceramic green sheet layer are uniformly dispersed, and the molten component of the second ceramic green sheet layer during heating Is preferable because it can suppress minute dimensional deformation accompanying the shape of the first ceramic green sheet layer and the conductor layer pattern formed thereon.

  The method for manufacturing an electronic component of the present invention will be described in detail below. FIGS. 1A to 1D are cross-sectional views for each process showing an example of an embodiment of an electronic component manufacturing method according to the present invention, wherein 1 is a support, 2 is a conductor layer, and 3 is a first ceramic. A rally, 4 is a second ceramic slurry, 5 is a laminated ceramic green sheet (hereinafter, the ceramic green sheet is also referred to as SG), 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 conductor paste obtained by pasting a conductor material powder by printing such as a screen printing method, a gravure printing method, an ink jet printing method, or a semi-additive method , Plating method such as additive method, method of processing metal foil such as subtracting method, method of directly forming metal film of predetermined pattern shape such as vapor deposition method on support 1, or conductor thick film formed in predetermined pattern shape by printing Or a metal foil processed into a predetermined pattern shape, or a method of transferring a metal film having a predetermined pattern shape formed by plating or vapor deposition 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 conductor powder, binder, solvent, etc., and adjusts the dispersibility of the conductor particles and the hardness and strength of the conductor layer 2. Therefore, a dispersant or a plasticizer may be added.

  Here, as the binder applied to the conductor paste, those conventionally used for the conductor paste can be used. For example, acrylic (acrylic acid, methacrylic acid or their homopolymer or copolymer) , Concretely acrylic acid ester copolymer, methacrylic acid ester copolymer, acrylic acid ester-methacrylic acid ester copolymer, etc.), polyvinyl butyral, polyvinyl alcohol, acrylic-styrene, polypropylene carbonate And homopolymers or copolymers of cellulose and cellulose. 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 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 is not particularly limited as long as the above-mentioned conductor powder and binder can be well dispersed and mixed, such as plasticizers such as terpineol, butyl carbitol acetate, and phthalic acid. Although usable, a low boiling point solvent such as terpineol is preferable in consideration of the drying property of the solvent after the formation of the conductor layer 2.

  The support 1 in the present invention is not particularly limited as long as it can form a conductor layer and a laminated SG, and polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate-isophthalate copolymer conventionally used. Resin, polyolefin resin such as polyethylene, polypropylene and polymethylpentene, polyfluorinated ethylene resin, cellulose resin, acrylic resin and other paper support such as fine paper and molded paper can be used. .

  A surface treatment layer such as a release layer may be formed on the surface of the support 1 forming the conductor layer 2 in order to improve the peelability from the support 1 after the formation of the laminated SG5. The types of release layers are broadly classified into silicone release agents and non-silicone release agents. As the non-silicone release agents, fluorine-based release agents can be used. As the release agent, any of a solventless type, an emulsion type, and a solvent type can be used depending on the product form. Further, the thickness of the release layer varies depending on the type of release agent used and the like, but when the laminated SG5 can be peeled off from the support 1 and the conductor layer is formed using a conductor paste, the release agent is used. Therefore, it is sufficient that the thickness of the conductor paste is such that no repelling of the conductor paste occurs when the conductor layer 2 is formed.

  When the conductor layer 2 is formed on the support 1, in order to facilitate the formation of the conductor layer 2, the support 1 can be subjected to a surface treatment to make the surface rough. 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 1 by mixing and embedding pores, inorganic particles, or the like in the support 1 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. 1B, the first ceramic slurry 3 is applied onto the support 1 on which the conductor layer 2 is formed, and then the first ceramic slurry 3 is applied as shown in FIG. The second ceramic slurry 4 is applied onto the ceramic slurry 3 and dried, thereby forming a laminated SG5 in which the second SG layer 4 ′ is formed on the first SG layer 3 ′. At this time, the difference between the solubility parameter of the first ceramic slurry 3 and the solubility parameter of the second ceramic slurry 4 is 2 or more. As a result, when the first ceramic slurry 3 is applied to the support 1 on which the conductor layer 2 is formed, and the second ceramic slurry 4 is applied onto the first ceramic slurry 3, the first and second ceramic slurries 3 are applied. Since the ceramic slurries 3 and 4 are prevented from dissolving with each other, the first SG layer 3 ′ and the second SG layer 4 ′ can be prevented from being mixed and made identical.

  Here, the solubility parameter is quantified based on the property that organic components having similar properties are easily compatible with each other, and is also called an SP value. Since those having similar solubility parameter values are easily dissolved, they are used as an index indicating the dissolving power of the organic component.

  The solubility parameter of the ceramic slurry of the present invention was calculated from the solubility parameter of each organic component in the ceramic slurry and the volume fraction of each organic component. For example, if the ceramic slurry contains two organic components, the solubility parameters are 5 and 7, and the volume fraction is 70% and 30%, respectively, the solubility parameter of the ceramic slurry is 5 × 0.7 + 7 X0.3 = 5.6. As the solubility parameter of the organic component of the present invention, solubility parameter data published by Kodansha “Solvent Handbook” (Shozo Asahara et al., 1976, first edition) was used.

  Further, the first ceramic slurry 3 is applied on the support 1 on which the conductor layer 2 is formed, and the second ceramic slurry 4 is applied on the applied first ceramic slurry 3 to form the laminated SG5. Therefore, the first SG layer 3 ′ and the second SG layer 4 ′ such as a high fluidity layer and a normal SG layer can be simultaneously formed. It is possible to form a high fluidity layer without causing problems such as longer time, higher cost, lower yield, and lower reliability of conductor connection between layers. As a result, since there is no lamination step of the high fluidity layer, it is possible to obtain a highly reliable electronic component free from delamination without air entrainment during the lamination of the high fluidity layer.

  The first and second ceramic slurries 3 and 4 in the present invention are a mixture of ceramic powder, binder, solvent and the like, and are used for adjusting the dispersibility of the ceramic powder and the hardness and strength of the laminated SG5. Or a plasticizer may be added. Moreover, the 1st ceramic slurry 3 contains the molten component which will be in a molten state at the time of a heating in the process of producing SG laminated body 6 mentioned later. These binder, solvent, plasticizer, and molten component are the respective organic components for calculating the solubility parameter described above.

Examples of the ceramic powder include Al ₂ O ₃ , AlN, glass ceramic powder (a mixture of glass powder and filler powder) and the like for a ceramic wiring board, and BaTiO ₃ and PbTiO ₃ systems for a multilayer capacitor. Composite perovskite-based ceramic powders, and the like, are selected as appropriate in accordance with characteristics required for electronic components.

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 for SG can be used. For example, acrylic (acrylic acid, methacrylic acid or their homopolymers or copolymers, specifically, Is acrylic acid ester copolymer, methacrylic acid ester copolymer, acrylic acid ester-methacrylic acid ester copolymer, etc.), polyvinyl butyral, polyvinyl alcohol, acrylic-styrene, polypropylene carbonate, cellulose Homopolymers or copolymers such as 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 SG layer 4 ′ is a molten state when heated when the SG laminate 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. Furthermore, 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. This is because when the material having a melting point in this range is used, the second SG layer 4 ′ is not softened and deformed at room temperature. Therefore, handling up to the stacking process is facilitated, and the SG stacked body 6 is manufactured. This is because organic components such as a binder and a plasticizer in the laminated SG5 are not decomposed during heating in the above, and thus delamination is not generated by the decomposition gas. 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 SG layer 4 ′ varies depending on the binder component to be used and the amount thereof and the molten component to be used, but the second SG layer 4 ′ is in a molten state in the molten component. Any amount may be used as long as it softens and comes into contact with the first SG layer 3 ′ of the stacked SG 5 positioned below and the conductor layer 2 embedded therein without a gap.

  Moreover, it is preferable that the addition amount of the binder contained in the 2nd ceramic slurry 4 is 19 to 40 mass%. The amount added here is the mass% of the binder contained in the second ceramic slurry 4 with respect to 100 mass% of the ceramic powder. If it is in this range, in the process of producing the SG laminate 6, the second SG layer of the laminate SG that is deformed following the shape of the conductor layer pattern formed thereon and is located below the second layer. It has sufficient peel strength with respect to 4 ', and can suppress the occurrence of blisters and pinholes due to the decomposition gas of the binder during firing.

  Further, the molecular weight of the binder contained in the second ceramic slurry 4 is preferably 80,000 to 300,000. If the molecular weight of the binder contained in the second ceramic slurry 4 is lower than 80,000, the fluidity of the binder becomes excessive, and the shape retention of the first SG layer 3 'cannot be obtained. Further, if the molecular weight of the binder contained in the second ceramic slurry 4 exceeds 300,000, the molten component contained in the second SG layer 4 ′ is not uniformly dispersed, and the laminated SG5 is heated to produce the second A sufficient amount of the molten component of the SG layer 4 ′ cannot be maintained, and pressure bonding cannot be performed with such a low pressure that the stacked SG is not distorted by pressurization.

  The acid value of the binder contained in the second ceramic slurry 4 is preferably 0.1 to 0.8 KOH mg / g. If the acid value of the binder contained in the second ceramic slurry 4 is lower than 0.1 KOHmg / g, the bondability between the inorganic powder and the binder becomes weak, and the inorganic powder and the binder are contained in the second SG layer 4 ′. It exists in a non-uniform state. Then, when the molten component contained in the second SG layer 4 ′ is not uniformly dispersed when heated, the stacked SG5 is heated to maintain a sufficient amount of the molten component in the second SG layer 4 ′. It is not possible to press-bond with a pressurizing force so low that the stacked SG is not distorted by pressurization. In addition, when the acid value of the binder contained in the second ceramic slurry 4 exceeds 0.8 KOHmg / g, the bondability between the inorganic powder and the binder becomes excessively strong, and the melt contained in the second SG layer 4 ′ When the components are melted by heating, they are not uniformly dispersed, and the stacked SG5 cannot be heated to maintain a sufficient amount of the melted component of the second SG layer 4 ′, and the stacked SG is not distorted by pressurization. Cannot be crimped with low pressure.

  Moreover, it is preferable that the glass transition point of the binder contained in the 2nd ceramic slurry 4 is -20 thru | or -12 degreeC. When the glass transition point is lower than −20 ° C., the soft property of the binder appears strongly at room temperature, so that the SG layers are difficult to be easily uneven with each other and adhesion between the stacked SGs occurs. When the glass transition point is higher than −12 ° C., softening of the stacked SG5 due to melting of the molten component during heating becomes insufficient, and the second SG layer 4 ′ is made to follow the shape of the first SG layer 3 ′ satisfactorily. It becomes difficult.

  Further, the hydroxyl value of the binder contained in the second ceramic slurry 4 is preferably 0.1 to 5 KOHmg / g. When the hydroxyl value of the binder contained in the second ceramic slurry 4 is lower than 0.1 KOHmg / g, the binding between the inorganic powder and the binder becomes weak, and the inorganic powder and the binder are contained in the second SG layer 4 ′. It exists in a non-uniform state. Therefore, the molten component contained in the second SG layer 4 ′ is not uniformly dispersed when melted by heating, and the laminated SG5 is heated to maintain a sufficient amount of the molten component of the second SG layer 4 ′. It is not possible to press-bond with a pressurizing force so low that the stacked SG is not distorted by pressurization. Moreover, when the hydroxyl value of the binder contained in the second ceramic slurry 4 exceeds 5 KOHmg / g, the bonding property between the inorganic powder and the binder becomes excessively strong, and the melting component contained in the second SG layer 4 ′ is increased. When melted by heating, the layer SG5 is not uniformly dispersed, and the melted component of the second SG layer 4 ′ cannot be maintained at a sufficient amount by heating, so that the layer SG5 is not distorted by pressurization. Cannot press with pressure.

  Moreover, it is preferable that the addition amount of the binder contained in the 1st ceramic slurry 3 is 10 to 20 mass%. The amount added here is mass% of the binder contained in the first ceramic slurry 3 with respect to 100 mass% of the ceramic powder. If the addition amount is less than 10% by mass, the density of the first SG layer 3 'made of the first ceramic slurry 3 is low, and the molten component in the second SG layer 4' is likely to diffuse. If it is more than 20% by mass, the drying time at the time of forming the ceramic green sheet becomes longer, so the drying time at the time of forming the SG becomes longer, and similarly, the molten component tends to diffuse. Therefore, the second SG layer 4 ′ cannot hold the amount of molten component necessary for deformation following the shape of the first SG layer 3 ′ when it is stacked, and delamination occurs.

  The molecular weight of the binder contained in the first ceramic slurry 3 is preferably 50,000 to 800,000. When the molecular weight of the binder added to the first ceramic slurry 3 is lower than 50,000, the first SG layer 3 ′ is deformed during the raw processing, resulting in large dimensional variations. In addition, when the molecular weight of the binder exceeds 800,000, the raw material components contained in the laminated SG5 are not uniformly dispersed due to the binding force with the binder, resulting in appearance defects such as pinholes in the first SG layer 3 ′. In addition, it causes insulation failure in the product.

  The acid value of the binder added to the first ceramic slurry 3 is preferably 0.1 to 5.0 KOHmg / g. If the acid value of the binder added to the first ceramic slurry 3 is lower than 0.1 KOHmg / g, the bondability between the inorganic powder and the binder becomes weak, and the first SG layer 3 ′ is deformed during raw processing. Dimensional variation becomes large. Moreover, when the acid value of the binder added to the first ceramic slurry 3 exceeds 5.0 KOHmg / g, the binding between the inorganic powder and the binder becomes excessively strong, thereby causing aggregation due to the bonding between the inorganic raw materials, Appearance defects such as pinholes occur in the first SG layer 3 ', which causes insulation defects in the product.

  Moreover, it is preferable that the glass transition point of the binder contained in the 1st ceramic slurry 3 is -20 thru | or 20 degreeC. Thereby, since the hard property of the binder appears strongly, the first SG layer 3 ′ becomes strong, and the molten component of the second SG layer 4 ′ follows the shape of the first SG layer 3 ′ during heating. Since the accompanying small dimensional deformation can be suppressed, it becomes more preferable. When the glass transition point is lower than −20 ° C., the soft nature of the binder appears strongly at room temperature, so that the stacked SG5s are not easily formed into the surface irregularities of each other, and the stacked SG5s are adhered or broken. When the glass transition point is higher than 20 ° C., the shape retention of the laminated SG5 is insufficient, and cracks, chips, etc. are likely to occur during handling.

  The hydroxyl value of the binder contained in the first ceramic slurry 3 is preferably 5 to 100 KOHmg / g. When the acid value of the binder contained in the first ceramic slurry 3 is lower than 5 KOHmg / g, the bonding property between the inorganic powder and the binder becomes weak, and the inorganic powder and the binder are not uniform inside the first SG layer 3 ′. It exists in the state. For this reason, the rough portion of the first SG layer 3 ′ is easily deformed when pressed and it is difficult to suppress dimensional deformation. Moreover, when the hydroxyl value of the binder contained in the first ceramic slurry 3 exceeds 100 KOH mg / g, the binding property of the binder becomes excessively strong, and the binder is bonded to each other without being bonded to the inorganic powder. The inorganic powder and the binder are present in a non-uniform state inside the layer 3 ′. Therefore, the rough portion of the second SG layer 3 ′ is easily deformed when pressed, and it is difficult to suppress dimensional deformation.

  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 by printing or press filling a conductor paste obtained by pasting a conductor material powder into a through hole formed in the multilayer SG5 by punching or laser processing. When the stacked SG5 is thick, the through hole processing is preferable because punching processing has no difference in the through hole diameters on the front and back of the stacked SG5. Moreover, when processing a through-hole, lamination | stacking SG5 may peel off from the support body 1, but it is more preferable to carry out with holding | maintaining on the support body 1, since the deformation | transformation of lamination | stacking SG5 can be prevented.

  As a method of forming the laminated SG5 by applying the first ceramic slurry 3 on the support 1 on which the conductor layer 2 is formed and applying the second ceramic slurry 4 on the applied first ceramic slurry 3. Examples include a doctor blade method, a lip coater method, a die coater method, and the like. As a method for applying the second ceramic slurry 4 onto the first ceramic slurry 3, particularly when an extrusion method such as a die coater method, a slot coater method, or a curtain coater method is used, these are non-contact type application methods. Since the method is used, the stacked SG5 may be formed without mixing the first ceramic slurry 3 and the second ceramic slurry 4 with a physical force.

  The thickness of the first SG layer 3 ′ is formed so as to be thicker than the thickness of the conductor layer 2 so that no gap is generated in the gap between the conductor layers 2 and the shape of the conductor layer 2 does not change. . The thickness of the second SG layer 4 ′ is such that the second SG layer 4 ′ is softened and the first SG layer 3 ′ of the stacked SG 5 positioned below the second SG layer 4 ′ and the conductor layer 2 embedded therein The thickness of the second SG layer 4 ′ should be smaller in order to suppress the deformation of the stacked SG5 as much as possible during the stacking. preferable.

  When an electronic component having a cavity is manufactured, a cavity-shaped through hole is formed in a part of the stacked SG 5 by punching with a mold or the like before the next step of manufacturing the SG stacked body 6.

  Next, as shown in FIG. 1 (d), the laminated SG5 stacked in alignment is heated to a temperature at which the molten component becomes molten and the second SG layer 4 'is softened and deformed, that is, the melting point of the molten component. SG laminated body 6 is produced by heating at about temperature. Here, it is also possible to peel off the laminated SG5 from the support 1 when laminating, and it is also possible to perform a treatment such as heating as necessary at this time. At this time, the softened second SG layer 4 ′ is pressed against the first SG layer 3 ′ and the conductor layer 2 formed in the second SG layer 4 ′ so that the stacked layers SG 5 are not displaced from each other. When pressure is applied to the extent that it is applied, more accurate and reliable crimping is possible. At this time, in order to improve the adhesiveness between the stacked SGs 5, an adhesive obtained by mixing a solvent with a binder, a plasticizer, or the like may be used.

  In the step of producing the SG laminate 6, the second SG layer 4 ′ contains a melting component that melts when heated, and therefore the second SG layer 4 ′ is heated when the laminated SG5 in which the conductor layer 2 is embedded is laminated and heated. Since the SG layer 4 ′ is softened, the second SG layer 4 ′ follows the surface shape composed of the first SG layer 3 ′ of the stacked SG 5 positioned below and the conductor layer 2 embedded therein. And deform. As a result, the stacked SGs 5 are brought into close contact with each other without generating voids around the conductor layer 2 or between the conductor layers 2, and delamination does not occur in the electronic component obtained by firing the SG stacked body 6.

  In addition, since the second SG layer 4 ′ contains a melting component that melts when heated, the second SG layer 4 ′ softens and has adhesiveness only by heating. There is no need for crimping. And since 1st SG layer 3 'formed by embedding the conductor layer 2 does not contain the fusion | melting component which melt | dissolves at the time of heating, 1st SG layer 3' did not deform | transform at the time of heating, and was laminated | stacked The stacked SG 5 is not deformed so that the second SG layer 4 ′ is softened to the first SG layer 3 ′ and the conductor layer 2 embedded in the second SG layer 4 ′ so as not to be misaligned. Therefore, the SG layer 6 that is obtained without deformation of the shape of the stacked SG 5 and the conductor layer 2 embedded in the stacked SG 5 and without distortion to the stacked SG 5 due to pressurization, and obtained by firing it. The obtained electronic component has high dimensional accuracy.

  For example, in the case of using a laminated SG that does not contain a melting component that melts when heated, the dimensional accuracy of the SG laminate 6 and the electronic component is about ± 0.5% (dimensional error). When the contained laminated SG5 was used, the dimensional accuracy of the SG laminated body 6 and the electronic component was about ± 0.2%, and it was proved by experiments that it was greatly improved.

  Further, when an electronic component having a cavity is manufactured, it is not necessary to press the laminated SG5 with a large pressure, so that the cavity bottom warps due to the difference in the elongation of the laminated SG5 due to the pressurization between the cavity peripheral part and the cavity bottom part. 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 SG located at the bottom of FIG. 1 (d), SG5 'composed of only the first SG5 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 SG5 in which the conductor layer 2 is not formed may be used for the multilayer SG5 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 SG 5 ′ may be used.

  On the second SG layer 4 ′ containing the molten component formed on the support 1, the first SG layer 3 ′ not containing the molten component is formed to form a stacked layer SG5. In the method of forming a conductor layer 2 on the second SG layer 4 'and then heating and laminating a plurality of laminated SG5s on which the conductor layer 2 is formed, delamination is prevented and electrons are not deformed by lamination pressure. Parts can be manufactured. In this method, the thickness of the second SG layer 4 ′ containing the molten component is required to be greater than or equal to the thickness of the conductor layer 2. Therefore, when the thickness of the laminated SG5 is thin, the laminated SG5 contains the molten component, that is, is deformed by heating. The proportion of the thickness of the second SG layer 4 ′ increases, and the entire stacked SG5 is easily deformed. On the other hand, in the manufacturing method of the present invention, the surface on which the conductor layer 2 of the laminated SG5 is formed is a substantially flat surface. Therefore, the second SG layer 4 deforms following the shape of this surface. 'The thickness can be reduced. Therefore, even when the thickness of the stacked SG5 is thin, it is more preferable because deformation of the stacked SG5 due to heating during stacking can be suppressed and high dimensional accuracy can be secured.

  Finally, the SG laminate 6 is fired to produce the electronic component of the present invention. The firing process consists of removing organic components and sintering the ceramic powder. The organic component is removed by heating the SG laminate 6 in a temperature range of 100 to 800 ° C., and the organic component is decomposed and volatilized. 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 the constrained green sheet is further laminated on the upper and lower surfaces of the SG 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. The constraining green sheet at this time also has a first SG layer 3 ′ and a second SG layer 4 ′ similar to the laminated SG5 of the present invention, and is also large when the constraining green sheet is laminated and pressure-bonded. No pressure is required, and the obtained electronic component may be of higher dimensional accuracy.

  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 SG5, in addition to the hardly sinterable inorganic component. This is because when the glass is softened and bonded to the laminated SG5 during firing, the bond between the laminated SG5 and the constraining green sheet becomes strong, 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.

  Examples of the present invention will be described in detail below.

  First, alumina powder and organic components as shown in Table 1 were mixed to prepare a first ceramic slurry and a second ceramic slurry. In order to confirm whether it was formed in two layers of the first SG layer and the second SG layer, an oxide of transition metal (chromium trioxide) was added to the first ceramic slurry.

  Next, the first ceramic slurry is applied on the PET film by a lip coater method to a thickness of 50 μm, and then the second ceramic slurry is applied on the applied first ceramic slurry by a die coater method to a thickness of 100 μm. The laminated SG was produced by applying and drying.

Only in Comparative Example 3 and Comparative Example 4, the laminated SGs were then laminated, and an SG laminate was produced by pressing at 80 ° C. and 0.5 MPa.

  When observing the cross section of the laminated body of the laminated SG of Comparative Example 1, the green color of chromium trioxide of the metal pigment is thin at the interface between the first SG layer and the second SG layer, and some diffusion is seen. However, it did not diffuse to the second SG layer, and two layers were properly formed.

  In the cross sections of the SG laminates of Comparative Examples 2 to 4, the first SG layer and the second SG layer that were neither diffused nor separated were formed. Moreover, in the SG laminated body of Example 4, although it observed to the cross section, it confirmed that it was able to laminate | stack without delamination.

  On the other hand, in Comparative Examples 1 and 2, the surface of the second SG layer is colored with chromium trioxide in green, and the first SG layer and the second SG layer are mixed and made identical. It was.

  Moreover, in the comparative example 3, when the cross section of SG laminated body was observed, peeling and delamination generate | occur | produced between SG layers.

  In this way, by separating the solubility parameter of the first ceramic slurry and the solubility parameter of the second ceramic slurry by two or more, the first SG layer and the second SG layer are prevented from being mixed and made identical. be able to.

  First, on a PET film as a support, a conductor paste containing tungsten as a main component was used and printed in a predetermined pattern with a thickness of 10 to 20 μm by a screen printing method to form a conductor layer.

  Next, for forming the first SG layer, 90% by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as sintering aids, and transition metal oxide (chromium trioxide) as coloring pigments are used. In addition, 10% by mass of a mixture of 10% by mass of methyl methacrylate resin as a binder and 10% by mass of dibutyl phthalate as a plasticizer was added to 100% by mass of ceramic powder, and toluene and acetic acid were added. Ethyl was used as a solvent and mixed for 40 hours by a ball mill to prepare a first ceramic slurry.

  Next, 90% by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, and calcia as sintering aids, and transition metal oxide (chromium trioxide) as a coloring pigment are used for forming the second SG layer. In total, blended at a ratio of 10% by mass, and methyl methacrylate resin as a binder with a solid content of 18, 19, 20, 25, 30, 35, 40, 42, 45% by mass with respect to 100% by mass of the ceramic powder. Externally added and formulated, hexadecanol as a melting component having a melting point of 35 to 100 ° C., 10% by mass in solid content, 1% by mass of dibutyl phthalate as a plasticizer, and toluene and ethyl acetate as solvent Was mixed by a ball mill for 40 hours to prepare a second ceramic slurry.

  Using a die coater sheet molding machine from these ceramic slurries, the first SG layer was molded at a thickness of 50 μm on a support on which a conductor layer was formed, at a molding speed of 2 m / min and a molding sheet width of 250 mm. On top, the second SG layer was formed as it was with a thickness of 100 μm to form a laminated SG.

  Four layers of the laminated SG on which the conductor layer was formed were stacked and heat-pressed at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce an SG laminate. The peel strength at that time was determined as a non-defective product when the peeled portion when the laminated SG was peeled was observed with a binocular microscope and the peeled portion was in the second SG layer.

Then, in order to remove organic components such as a binder in the obtained SG 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. A cross section of this sintered body was observed, and the presence or absence of delamination between the ceramic layers and the occurrence of bumps or pinholes was investigated. Table 2 shows the evaluation results according to the amount of binder in the second ceramic slurry.

In addition, “◯” in the column of peel strength in Table 2 indicates that the peeled portion was in the first SG layer when the laminate was peeled off. “Δ” indicates that it was out of the first SG layer. “◯” 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 SG laminate, delamination was observed inside the sintered body. “◯” in the column of the presence / absence of buku / pinhole indicates that there is no buku or pinhole inside the sintered body. “Δ” indicates that although there was no problem in the formation of the laminate, burr and pinholes were observed inside the sintered body.

  From Table 2, sample No. whose addition amount of the said binder is less than 19 mass% is shown. In No. 1, the peeled portion was outside the first SG layer, and delamination occurred inside the sintered body. In addition, Sample No. in which the addition amount of the binder is larger than 40% by mass. In Nos. 8 and 9, bobs and pinholes occurred in the inner layer.

  On the other hand, sample No. with the addition amount of the said binder of 19 to 40 mass%. Nos. 2, 3, 4, 5, 6, and 7 were excellent in that the peeled portion was in the first SG layer and there was no delamination, and no blemish or pinhole was generated in the inner layer.

  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 forming the first SG layer, 90% by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as sintering aids, and transition metal oxide (chromium trioxide) as coloring pigments are used. In addition, 10% by weight of a mixture was prepared, and 10% by weight of a methyl methacrylate resin as a binder and 10% by weight of dibutyl phthalate as a plasticizer were added to 100% by weight of ceramic powder. Ethyl was used as a solvent and mixed for 40 hours by a ball mill to prepare a first ceramic slurry.

  Next, for the formation of the second SG layer, 90% 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. It is formulated at a ratio of 10% by mass, and 20% by mass of methyl methacrylate resin as a solid content as a binder with respect to 100% by mass of ceramic powder, and the molecular weight of methyl methacrylate resin is 40,000, 80,000, 100,000, 200,000, 300, 360,000 and 500,000, respectively, melting point of 35 to 100 ° C. as a melting component, hexadecanol as a solid component, 10% by mass in solid content, dibutyl phthalate as a plasticizer, and 1% by mass outside addition, toluene Then, a second ceramic slurry was prepared by mixing for 40 hours with a ball mill using ethyl acetate as a solvent.

  Using a die coater sheet molding machine from these ceramic slurries, the first SG layer was molded at a thickness of 50 μm on a support on which a conductor layer was formed, at a molding speed of 2 m / min and a molding sheet width of 250 mm. On top, the second SG layer was formed as it was with a thickness of 100 μm to form a laminated SG.

  Four layers of the laminated SG on which the conductor layer was formed were stacked and heat-pressed at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce an SG laminate. Then, the dimension of the completed SG laminated body was measured with the three-dimensional measuring device.

Then, in order to remove organic components such as a binder in the obtained SG 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 presence or absence of delamination between the ceramic layers was investigated. Table 3 shows the evaluation results by molecular weight of the binder in the second ceramic slurry.

In Table 3, “◯” in the column of 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 SG laminate, delamination was observed inside the sintered body. Further, “◯” in the column of the lamination dimension indicates that the dimension variation was smaller than ± 0.05% as a result of measuring the dimension after lamination with a three-dimensional measuring machine. “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. In No. 1, delamination occurred in the sintered body, and the dimensional variation in the lamination dimension was 0.05% or more. In addition, sample no. In Nos. 5 and 6, 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. with a molecular weight of the above binder of 80,000 to 300,000. Nos. 2, 3 and 4 had no inner layer delamination and were excellent in terms of dimensional variation.

  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 forming the first SG layer, 90% by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as sintering aids, and transition metal oxide (chromium trioxide) as coloring pigments are used. In combination, 10% by mass of a ceramic powder, 20% by mass of a methyl methacrylate resin as a binder and 100% by mass of a ceramic powder, 10% by mass of hexadecanol as a low melting point component, and a plasticizer As a starting material, 1% by weight of dibutyl phthalate was added, and toluene and ethyl acetate were used as a solvent and mixed for 40 hours by a ball mill to prepare a first ceramic slurry.

  Next, 90% by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, and calcia as sintering aids, and transition metal oxide (chromium trioxide) as a coloring pigment are used for forming the second SG layer. In combination, 10% by mass is prepared, and 10% by mass of the methyl methacrylate resin as a solid content as a binder with respect to 100% by mass of the ceramic powder, and the acid value of the binder is 0.0, 0.1, 0.5, Prepared respectively as 0.8, 0.9, 1.5 KOHmg / g, 10% by mass of hexadecanol as a melting component having a melting point of 35 to 100 ° C. in solid content, and 1% by mass of dibutyl phthalate as a plasticizer Externally added and mixed with a ball mill for 40 hours using toluene and ethyl acetate as a solvent to prepare a second ceramic slurry.

  From these ceramic slurries, a die coater sheet molding machine was used to mold the first SG layer with a thickness of 50 μm on a support on which a conductor layer was formed, at a molding speed of 2 m / min and a molding sheet width of 250 mm. Then, the second SG layer was formed as it was with a thickness of 100 μm to form a laminated SG.

  Four layers of the laminated SG on which the conductor layer was formed were stacked and heat-pressed at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce an SG laminate. Then, the dimension of the completed SG laminated body was measured with the three-dimensional measuring device.

Then, in order to remove organic components such as a binder in the obtained SG 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. Observation of the cross section of this sintered body and the presence or absence of delamination between the ceramic layers were investigated. Table 4 shows the evaluation results by acid value of the binder in the second SG layer.

In Table 4, “◯” in the column of 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 SG laminate, delamination was observed inside the sintered body. Further, “◯” in the column of the lamination dimension indicates that the dimension variation was smaller than ± 0.05% as a result of measuring the dimension after lamination with a three-dimensional measuring machine. “Δ” indicates that although there was no problem in the product dimensions, the dimensional variation was ± 0.05% or more.

  From Table 4, sample No. whose acid value of the said binder is less than 0.1 KOHmg / g. In No. 1, delamination occurred in the sintered body, and the dimensional variation in the lamination dimension was 0.05% or more. In addition, Sample No. in which the acid value of the binder is larger than 0.8 KOH mg / g. In Nos. 5 and 6, bumps and pinholes occurred in the inner layer.

  On the other hand, Sample No. with the acid value of the said binder 0.1-0.8 mass%. Nos. 2, 3 and 4 had no inner layer delamination and were excellent in terms of dimensional variation.

  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 by a screen printing method using a conductive paste containing tungsten as a main component on a PET film as a support. .

  Next, for the formation of the first SG layer, 90% 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, 8%, 10, 12, 14, 16, 18, 20, 22, 24% by mass of isobutyl methacrylate resin as a binder with respect to 100% by mass of ceramic powder prepared at a ratio of 10% by mass. Each was prepared and added externally, and toluene and ethyl acetate were mixed as a solvent by a ball mill for 40 hours to prepare a first ceramic slurry.

  Next, 90% by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, and calcia as sintering aids, and transition metal oxide (chromium trioxide) as a coloring pigment are used for forming the second SG layer. 10 mass% of hexamethanol as a melting component having a melting point of 35 to 100 ° C. with a methyl methacrylate resin as a solid content of 10 mass% with respect to 100 mass% of ceramic powder prepared at a ratio of 10 mass% in total. 1% by weight of dibutyl phthalate was added as a plasticizer and mixed with a ball mill using toluene and ethyl acetate as a solvent for 40 hours to prepare a second ceramic slurry.

  From these slurries, a die coater sheet molding machine was used to mold the first SG layer with a thickness of 50 μm on a support on which a conductor layer was formed at a molding speed of 2 m / min and a molding sheet width of 250 mm. The second SG layer was formed with a thickness of 50 μm as it was to form a laminated SG.

Each of the laminated SGs on which the conductor layers were formed was superposed on each other and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce an SG laminate. Then, in order to remove organic components such as a binder in the obtained SG 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 presence or absence of delamination between the ceramic layers was investigated. Table 5 shows the evaluation results according to the amount of binder in the first ceramic slurry.

In Table 5, “◯” in the column of 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 SG laminate, delamination was observed inside the sintered body.

  From Table 5, sample No. whose addition amount of the said binder is less than 10 mass%. In No. 1, delamination occurred inside the sintered body. In addition, Sample No. in which the addition amount of the binder is larger than 20% by mass. In 8 and 9, similarly, delamination occurred in the sintered body.

  On the other hand, the sample No. with the added amount of the binder of 10 to 20 mass%. Nos. 2, 3, 4, 5, 6 and 7 were excellent without inner layer delamination.

  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 formation of the first SG layer, 90% 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, In addition, 10% by mass of isobutyl methacrylate resin as a binder is added to 100% by mass of the ceramic powder prepared at a ratio of 10% by mass, and the molecular weight of the binder is 10,000, 50,000, and 20 at that time. 1 million, 400,000, 600,000, 800,000, and 1 million were prepared, respectively, and mixed with a ball mill for 40 hours using toluene and ethyl acetate as a solvent to prepare a first ceramic slurry.

  Next, 90% by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, and calcia as sintering aids, and transition metal oxide (chromium trioxide) as a coloring pigment are used for forming the second SG layer. A total of 10% by weight of a methyl methacrylate resin as a binder is added to 100% by weight of the ceramic powder prepared at a ratio of 10% by weight. After adding 10% by weight of hexadecanol as a melting component at 100 ° C. and adding 1% by weight of dibutyl phthalate as a plasticizer, the mixture is mixed for 40 hours by a ball mill using toluene and ethyl acetate as a solvent. A ceramic slurry was prepared.

  From these slurries, a die coater sheet molding machine was used to mold the first SG layer with a thickness of 50 μm on a support on which a conductor layer was formed at a molding speed of 2 m / min and a molding sheet width of 250 mm. The second SG layer was formed with a thickness of 50 μm as it was to form a laminated SG.

  Each of the laminated SGs on which the conductor layers were formed was superposed on each other and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce an SG laminate. Then, the dimension of the completed SG laminated body was measured with the three-dimensional measuring device.

Then, in order to remove organic components such as a binder in the obtained SG laminate and carbon remaining after the organic components are 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 presence or absence of delamination between the ceramic layers was investigated. Table 6 shows the evaluation results of the binders in the first ceramic slurry classified by molecular weight.

In Table 6, “◯” 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. Further, “◯” in the column of the lamination dimension indicates that the dimension variation was smaller than ± 0.05% as a result of measuring the dimension after lamination with a three-dimensional measuring machine. “Δ” indicates that although there was no problem in the product dimensions, the dimensional variation was ± 0.05% or more.

  From Table 6, the sample No. with a molecular weight of the binder of less than 50,000 is shown. In No. 1, delamination occurred in the sintered body, and the dimensional variation in the lamination dimension was 0.05% or more. In addition, sample no. In Nos. 6 and 7, delamination occurred in the sintered body, and the dimensional variation in the lamination dimension was 0.05% or more.

  On the other hand, sample Nos. With a binder molecular weight of 50,000 to 800,000 were used. 2, 3, 4 and 5 had no inner layer delamination and were excellent in dimensional variation.

  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 formation of the first SG layer, 90% 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, In addition, 10% by mass of isobutyl methacrylate resin as a binder is added to 100% by mass of the ceramic powder prepared at a ratio of 10% by mass, and the acid value of the binder is 0.0, 0.0. The first ceramic slurry was prepared by mixing at 1,0.5, 1.0, 5.0, and 8.0 KOH mg / g, respectively, and mixing with toluene and ethyl acetate for 40 hours by a ball mill.

  Next, 90% by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, and calcia as sintering aids, and transition metal oxide (chromium trioxide) as a coloring pigment are used for forming the second SG layer. 10 mass% of hexamethanol as a melting component having a melting point of 35 to 100 ° C. with a methyl methacrylate resin as a solid content of 10 mass% with respect to 100 mass% of ceramic powder prepared at a ratio of 10 mass% in total. 1% by weight of dibutyl phthalate was added as a plasticizer and mixed with a ball mill using toluene and ethyl acetate as a solvent for 40 hours to prepare a second ceramic slurry.

  From these slurries, a die coater sheet molding machine was used to mold the first SG layer with a thickness of 50 μm on a support on which a conductor layer was formed at a molding speed of 2 m / min and a molding sheet width of 250 mm. The second SG layer was formed with a thickness of 50 μm as it was to form a laminated SG. The laminated SG after molding was evaluated for the presence or absence of pinholes in the laminated SG by visual inspection using oblique light.

Each of the laminated SGs on which the conductor layers were formed was superposed on each other and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce an SG laminate. Then, in order to remove organic components such as a binder in the obtained SG laminate and carbon remaining after the organic components are 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 presence or absence of delamination between the ceramic layers was investigated. Table 7 shows the evaluation results by acid value of the binder in the first ceramic slurry.

In Table 7, “◯” in the column of 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 SG laminate, delamination was observed inside the sintered body. In addition, “◯” in the column of the presence / absence of pinholes in the sheet indicates that there was no pinhole in the laminated SG after molding, which was excellent. “Δ” indicates that there is no pinhole in the product, but a pinhole is confirmed in the stacked SG.

  From Table 7, sample No. whose acid value of the said binder is less than 0.1 KOHmg / g. In No. 1, delamination occurred in the sintered body, and pinholes were confirmed in the laminated SG. In addition, Sample No. whose acid value of the binder is larger than 5.0 KOHmg / g. In No. 6, delamination occurred in the sintered body, and pinholes were confirmed in the laminated SG.

  On the other hand, Sample No. with the acid value of the binder being 0.1 to 5.0 KOHmg / g. Nos. 2, 3, 4 and 5 had no inner layer delamination and had excellent dimensional variations.

  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. .

  Next, for forming the first SG layer, 90% by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as sintering aids, and transition metal oxide (chromium trioxide) as coloring pigments are used. Combined with 10% by mass of ceramic powder, 10% by mass of methyl methacrylate as a binder was added to the ceramic powder at 100% by mass and added externally, and 1% by mass of dibutyl phthalate was added as a plasticizer. The slurry was added and mixed with a ball mill for 40 hours using toluene and ethyl acetate as a solvent to prepare a slurry.

  Next, 90% by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, and calcia as sintering aids, and transition metal oxide (chromium trioxide) as a coloring pigment are used for forming the second SG layer. In total, the mixture was prepared at a ratio of 10% by mass. To 100% by mass of the ceramic powder, 20% by mass of methyl methacrylate-ethyl acrylate copolymer resin was added as a binder in the solid content, and methyl methacrylate-acrylic acid was added. The glass transition points of the ethyl copolymer resin are respectively prepared at −22, −20, −15, −12, −10, −7 ° C., and hexadecanol is a solid component as a melting component having a melting point of 35 to 100 ° C. 10% by weight, 1% by weight of dibutyl phthalate was added as a plasticizer, and toluene and ethyl acetate were used as solvents and mixed for 40 hours by a ball mill to prepare a slurry.

  From these slurries, a die coater sheet molding machine was used to mold the first SG layer with a thickness of 50 μm on a support on which a conductor layer was formed, at a molding speed of 2 m / min and a molding sheet width of 250 mm. Then, the second SG layer was formed as it was with a thickness of 100 μm to form a laminated SG. Four laminated layers SG 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 prepare an SG laminated body.

Then, in order to remove organic components such as a binder in the obtained SG 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 to investigate whether delamination occurred between the ceramic layers. Table 8 shows the evaluation results for each glass transition point of the binder in the second ceramic slurry.

In addition, “◯” in the column of sheet adhesion in Table 8 indicates that when the stacked SGs are handled at room temperature, the stacked SGs do not adhere to each other and the handling is easy. “Δ” indicates that the stacked SGs adhere to each other only when they are stacked at room temperature and are difficult to handle. “◯” 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 SG laminate, delamination was observed inside the sintered body.

  From Table 8, Sample No. whose glass transition point of the said binder is less than -20 degreeC is shown. In No. 1, sheet adhesion occurred. In addition, Sample No. with a glass transition point of the binder of greater than −12 ° C. In Nos. 5 and 6, delamination occurred in the sintered body.

  On the other hand, sample No. 2 having a glass transition point of −200,000 to −12 ° C. of the binder. 2, 3 and 4 were excellent without inner layer delamination.

  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 forming the first SG layer, 90% by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as sintering aids, and transition metal oxide (chromium trioxide) as coloring pigments are used. In combination, 10% by mass of the ceramic powder, 20% by mass of a methyl methacrylate resin as a binder, and 1% by mass of dibutyl phthalate as a plasticizer are added to 100% by mass of the ceramic powder. A first ceramic slurry was prepared by mixing for 40 hours with a ball mill using ethyl acetate as a solvent.

  Next, 90% by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, and calcia as sintering aids, and transition metal oxide (chromium trioxide) as a coloring pigment are used for forming the second SG layer. In total, the mixture was prepared at a ratio of 10% by mass, and 10% by mass of a methyl methacrylate resin as a binder was added as a binder to 100% by mass of the ceramic powder. Prepared at 1,2,4,5,7KOHmg / g, respectively, hexadecanol as a melting component with a melting point of 35 to 100 ° C. as a solid component, and 10% by mass of dibutyl phthalate as a plasticizer. The mixture was added and mixed with a ball mill for 40 hours using toluene and ethyl acetate as a solvent to prepare a second ceramic slurry.

  Using a die coater sheet molding machine from these ceramic slurries, the first SG layer was molded at a thickness of 50 μm on a support on which a conductor layer was formed, at a molding speed of 2 m / min and a molding sheet width of 250 mm. On top, the second SG layer was formed as it was with a thickness of 100 μm to form a laminated SG.

Four laminated layers SG 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 prepare an SG laminated body. Then, in order to remove organic components such as a binder in the obtained SG 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 to investigate the presence or absence of delamination between the ceramic layers. Table 9 shows the evaluation results for the hydroxyl value of the binder in the second ceramic slurry.

In Table 9, “◯” 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 SG laminate, delamination was observed inside the sintered body.

  From Table 9, sample No. whose hydroxyl value of the binder is less than 0.1 KOHmg / g. In No. 1, delamination occurred inside the sintered body. In addition, Sample No. with a hydroxyl value of the binder being greater than 5 KOHmg / g. In No. 6, bobs and pinholes occurred in the inner layer.

  On the other hand, Sample No. with the hydroxyl value of the binder being 0.1 to 5 KOHmg / g. 2, 3, 4 and 5 were excellent without inner layer delamination.

  In the same manner as in Example 9, 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 forming the first SG layer, 90% by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as sintering aids, and transition metal oxide (chromium trioxide) as coloring pigments are used. In addition, 10% by mass of a methyl methacrylate-ethyl acrylate copolymer resin as a binder was added as a binder to 100% by mass of the ceramic powder. The glass transition points of the ethyl acrylate copolymer resin were respectively prepared at −22, −20, −15, −12, −10, −7 ° C., 1% by mass of dibutyl phthalate was added as a plasticizer, and toluene was added. Then, a first ceramic slurry was prepared by mixing for 40 hours with a ball mill using ethyl acetate as a solvent.

  Next, 90% by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, and calcia as sintering aids, and transition metal oxide (chromium trioxide) as a coloring pigment are used for forming the second SG layer. Combined, blended at a ratio of 10% by mass, and blended with 20% by mass of a methyl methacrylate resin as a binder with respect to 100% by mass of the ceramic powder, added externally, and melted at a melting point of 35 to 100 ° C. 10% by mass of hexadecanol as a solid component and 1% by mass of dibutyl phthalate as a plasticizer were externally added and mixed with a ball mill using toluene and ethyl acetate as a solvent for 40 hours to prepare a second ceramic slurry. .

  Using a die coater sheet molding machine from these ceramic slurries, the first SG layer was molded at a thickness of 50 μm on a support on which a conductor layer was formed, at a molding speed of 2 m / min and a molding sheet width of 250 mm. On top, the second SG layer was formed as it was with a thickness of 100 μm to form a laminated SG.

Four laminated layers SG 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 prepare an SG laminated body. Then, in order to remove organic components such as a binder in the obtained SG 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 to investigate the presence or absence of delamination between the ceramic layers. Table 10 shows the evaluation results for each glass transition point of the binder in the first ceramic slurry.

In addition, “◯” in the column of sheet adhesion in Table 10 indicates that when the stacked SGs were handled at room temperature, the stacked SGs did not adhere to each other and the handling was easy. “Δ” indicates that the stacked SGs adhere to each other only when they are stacked at room temperature and are difficult to handle. “◯” in the column of the sheet crack and chip indicates that the stack SG was easy to handle without cracking or chipping when handled at room temperature. “Δ” indicates that the laminate SG was cracked or chipped when handled at room temperature and was difficult to handle. “◯” 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 SG laminate, delamination was observed inside the sintered body.

  From Table 10, Sample No. whose glass transition point of the said binder is less than -20 degreeC. In No. 1, sheet adhesion occurred. In addition, Sample No. with a glass transition point of the binder higher than 20 ° C. In Nos. 5 and 6, sheet cracking or chipping occurred.

  On the other hand, Sample No. with a glass transition point of the above binder of 0.1 to 5 KOHmg / g. Nos. 2, 3 and 4 were excellent with no sheet adhesion, no cracking or chipping and no inner layer delamination.

  In the same manner as in Example 10, 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 forming the first SG layer, 90% by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, calcia as sintering aids, and transition metal oxide (chromium trioxide) as coloring pigments are used. In total, the mixture was formulated at a ratio of 10% by mass. To 100% by mass of the ceramic powder, 10% by mass of a methyl methacrylate resin as a binder was added as a binder, and the hydroxyl value of the binder was adjusted to 0.0, 3, 5,10,20,40,60,80,100,104,110KOHmg / g respectively, add 1% by weight of dibutyl phthalate as a plasticizer, and mix for 40 hours with toluene and ethyl acetate as solvent The first ceramic slurry was prepared.

  Next, 90% by mass of alumina having an average particle diameter of 1 μm, silica, magnesia, and calcia as sintering aids, and transition metal oxide (chromium trioxide) as a coloring pigment are used for forming the second SG layer. Combined, the ratio is 10% by mass. Based on 100% by mass of the ceramic powder, 20% by mass of methyl methacrylate resin as a binder is solid, and hexadecanol is solid as a melting component having a melting point of 35 to 100 ° C. 10% by mass and 1% by mass of dibutyl phthalate as a plasticizer were added and mixed with a ball mill using toluene and ethyl acetate as a solvent for 40 hours to prepare a second ceramic slurry.

  From these slurries, a die coater sheet molding machine was used to mold the first SG layer with a thickness of 50 μm on a support on which a conductor layer was formed, at a molding speed of 2 m / min and a molding sheet width of 250 mm. Then, the second SG layer was formed as it was with a thickness of 100 μm to form a laminated SG.

Four laminated layers SG 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 prepare an SG laminated body. Then, the dimension of the completed SG laminated body was measured with the three-dimensional measuring device. Then, in order to remove organic components such as a binder in the obtained SG 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 to investigate the presence or absence of delamination between the ceramic layers. Table 11 shows the evaluation results by hydroxyl value of the binder in the first ceramic slurry.

In Table 11, “◯” in the column of 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 SG laminate, delamination was observed inside the sintered body. “◯” 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 less 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 11, Sample No. whose hydroxyl value of the binder is less than 5 KOHmg / g. In Nos. 1 and 2, delamination did not occur inside the sintered body, but the dimensional variation in the lamination dimension was 0.05% or more. In addition, Sample No. with a hydroxyl value of the binder greater than 100 KOHmg / g. No. 11 similarly had no delamination inside the sintered body, but 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 of the binder was used. Nos. 3, 4, 5, 6, 7, 8, 9, and 10 had no inner layer delamination and were excellent in dimensional variation.

  The present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the scope of the present invention. For example, in the above-described embodiment, a ceramic slurry was prepared by adding and mixing an inorganic powder, a binder, and a solvent, but a plasticizer may be added to impart flexibility to the laminated SG. 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 slurry 4 ... 2nd ceramic slurry 5 ... Laminated ceramic green sheet 6 ... Ceramic green sheet laminated body

Claims (12)

Forming a conductor layer on the support, applying a first ceramic slurry on the support on which the conductor layer is formed, and applying a second ceramic slurry on the applied first ceramic slurry. A step of drying to form a multilayer ceramic green sheet comprising the conductor layer and the first and second ceramic green sheet layers; and laminating a plurality of the multilayer ceramic green sheets and heating the ceramic green sheets And a step of firing the ceramic green sheet laminate, and the second ceramic slurry is a molten component that is in a molten state upon heating when the ceramic green sheet laminate is produced. The solubility parameter of the first ceramic slurry and the second ceramic slurry Method of manufacturing an electronic component, wherein a difference between Kaido parameter is two or more. 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 slurry is 19 to 40% by mass. The method of manufacturing an electronic component according to any one of claims 1 to 3, wherein the organic binder contained in the second ceramic slurry has a molecular weight of 80,000 to 300,000. 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 slurry is 0.1 to 0.8 KOH mg / g. 6. The method for manufacturing an electronic component according to any one of claims 1 to 5, wherein an addition amount of the organic binder contained in the first ceramic slurry is 10 to 20% by mass. The method of manufacturing an electronic component according to claim 1, wherein the organic binder contained in the first ceramic slurry has a molecular weight of 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 slurry is 0.1 to 5.0 KOH mg / g. 9. 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 slurry is −20 to −12 ° C. 10. 10. The method of manufacturing an electronic component according to claim 1, wherein the organic binder contained in the second ceramic slurry has a hydroxyl value of 0.1 to 5 KOH mg / g. The method of manufacturing an electronic component according to any one of claims 1 to 10, wherein a glass transition point of the organic binder contained in the first ceramic slurry is -20 to 20 ° C. 12. The method of manufacturing an electronic component according to claim 1, wherein the organic binder contained in the first ceramic slurry has a hydroxyl value of 5 to 100 KOHmg / g.

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