JP2005277166A - Method for manufacturing electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an electronic component that is free from delamination and high in reliability and dimentional accuracy. <P>SOLUTION: The method for manufacturing an electronic component is provided with a step for forming a first ceramic green sheet layer 2, a step wherein ceramic slurry 3 is spread on the first ceramic green sheet layer 2, drying is performed, a second ceramic green sheet layer 3' is formed and a ceramic green sheet 4 is formed, a step for forming a conductor layer 5 on the ceramic green sheet 4, a step wherein a plurality of the ceramic green sheets 4 on which the conductor layers 5 were formed are laminated and heated, and a ceramic green sheet lamination 6 is formed, and a step for baking the ceramic green sheet lamination 6. Furthermore, difference between solubility parameter of the first ceramic green sheet layer 2 and solubility parameter of the ceramic slurry 3 is at least 3 and at most 8. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

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

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

  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. Therefore, it tends to be insufficient crimping. As a result, when such a laminate is fired, there is a problem in that delamination (delamination) occurs at a portion where the pressure bonding is insufficient.

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

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

  In addition, when another green sheet is laminated on the conductor layer formed on the green sheet, the green sheet hardly follows the cross-sectional shape of the conductor layer, so that a void is generated around the conductor layer. There is a problem that delamination is likely to occur.

  To solve this problem, Patent Document 2 proposes that a ceramic layer containing a resin binder of 78% by volume or more with respect to the ceramic powder is provided on at least one side of the green sheet, and an internal conductor layer is formed on the upper surface. Has been. 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.
Japanese Patent No. 3344100 JP 61-229551 A

  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 the method (Method B) was such that a slurry that would become a ceramic layer was applied and dried 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, there is no increase in the number of layers, and the number of steps is small compared to Method A, and there is no increase in the number of layers, so there is no decrease in stacking reliability. There is a problem that a normal green sheet under the solvent dissolves due to the solvent in the inside, or the close contact between the high fluidity layer and the lower green sheet becomes insufficient, and peeling or voids are generated.

  Further, in the conventional method using a laminate having a high fluidity portion, a high pressure of, for example, 180 MPa is applied in the thickness direction in order to perform pressure bonding so that the high fluidity portion is moved and delamination does not occur. There is a need. When such a high pressure is applied to the green sheet on which the conductor layer is formed, the shape of the green sheet or the conductor pattern is deformed. As a result, it is difficult to mount components on the board because the desired dimensional accuracy of the board cannot be obtained, and the conductor pattern shape as designed cannot be obtained. There is a problem that electrical characteristics such as the above cannot be obtained. Furthermore, the problem of the gap generated between the wiring conductor layers when the spacing between the wiring conductor layers is fine remains unsolved.

  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 particular, when the cavity bottom is thin in a package having a cavity, the cavity bottom is easily deformed. 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 is highly adhesive at room temperature, so it is not easy to handle, and therefore air is involved during lamination. Delamination may occur because it is easy.

  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 crimping, and the lean sheet around the cavity extends due to pressurization, while no pressure is applied to the bottom of the cavity, so the green sheet at the bottom of the cavity By being pushed from. This is more likely to occur when the electronic component is smaller and the cavity bottom is thinner. If the cavity bottom warps, it becomes difficult to mount an electronic element such as a crystal resonator or an IC chip. Even if it can be mounted, the mounted components are tilted. Therefore, when an optical semiconductor element such as a CCD or C-MOS is mounted, there is a problem that the light receiving accuracy deteriorates.

  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 of manufacturing an electronic component that has no delamination and has high reliability and high dimensional accuracy.

  The method for manufacturing an electronic component of the present invention includes a step of forming a first ceramic green sheet layer, and applying a ceramic slurry on the first ceramic green sheet layer and drying to form a second ceramic green sheet layer. Forming a ceramic green sheet, forming a conductor layer on the ceramic green sheet, laminating a plurality of the ceramic green sheets on which the conductor layer is formed, and heating the ceramic green sheet laminate And a step of firing the ceramic green sheet laminate, wherein the difference between the solubility parameter of the first ceramic green sheet layer and the solubility parameter of the ceramic slurry is 3 to 8 It is characterized by this.

  In the method of manufacturing an electronic component according to the present invention, preferably, the first ceramic green sheet layer contains a molten component that is in a molten state when heated when the ceramic green sheet laminate is produced. It is a feature.

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

  In the present invention, it is preferable that the amount of the organic binder contained in the first ceramic green sheet layer is 19 to 30 parts by mass with respect to 100 parts by mass of the ceramic powder.

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

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

  In the present invention, it is preferable that the organic binder added in the ceramic slurry to be the second ceramic green sheet layer is 10 to 19 parts by mass with respect to 100 parts by mass of the ceramic powder.

  In the present invention, it is preferable that the molecular weight of the organic binder contained in the ceramic slurry to be the second ceramic green sheet layer is 100,000 to 800,000.

  In the present invention, preferably, the acid value of the organic binder contained in the ceramic slurry to be the second ceramic green sheet layer 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 green sheet layer is −20 to 0 ° C.

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

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

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

  According to the method of manufacturing an electronic component of the present invention, a step of forming a first ceramic green sheet layer, and applying a ceramic slurry on the first ceramic green sheet layer and drying the second ceramic green sheet layer Since the ceramic green sheet is formed, the formation of the second ceramic green sheet layer as the high fluidity layer and the lamination on the first ceramic green sheet layer as the normal ceramic green sheet layer are performed simultaneously. Since there is no process for drilling high-fluidity green sheets and laminating high-fluidity green sheets, there is an increase in the number of layers, resulting in longer construction periods, higher costs, lower yields, and reliable conductor connection between layers It is possible to form a high fluidity layer without causing problems such as low No entrainment of air at the time of stacking of sexual layer, it is possible to obtain an electronic component without delamination reliability.

  In addition, since the difference between the solubility parameter of the first ceramic green sheet layer and the solubility parameter of the ceramic slurry is 3 to 8, when the ceramic slurry is applied on the first ceramic green sheet layer, the first ceramic Since it suppresses that a green sheet layer and a ceramic slurry melt | dissolve in each other, it can prevent that a 1st ceramic green sheet layer and a 2nd ceramic green sheet layer mix and make it the same, and a 1st ceramic Since the ceramic slurry is not repelled on the green sheet layer, the ceramic slurry is uniformly applied to the entire surface, and a uniform second ceramic green sheet layer without peeling or voids can be formed.

  According to the method for manufacturing an electronic component of the present invention, preferably, the first ceramic green sheet layer contains a melting component that melts when heated when the ceramic green sheet laminate is produced. The first ceramic green sheet layer containing the molten component and the second ceramic green sheet layer not containing the molten component are formed. When the ceramic green sheet on which the conductor layer is formed is laminated and heated, the first ceramic green sheet layer is heated. Since the first ceramic green sheet layer is softened, the first ceramic green sheet layer follows the shape of the second ceramic green sheet layer of another ceramic green sheet located below and the shape of the conductor pattern formed thereon. Will be deformed. As a result, the 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 first ceramic green sheet layer contains a melting component that melts when heated, the first ceramic green sheet layer is softened and has adhesiveness only by heating. There is no need to crimp ceramic green sheets. And since the 2nd ceramic green sheet layer in which a conductor pattern is formed does not contain the fusion | melting component which fuse | melts at the time of a heating, a 2nd ceramic green sheet layer does not deform | transform at the time of a heating, The laminated | stacked ceramic green sheet has In order to prevent misalignment, the softened first ceramic green sheet layer is deformed following the shape of another second ceramic green sheet layer located below and the conductor pattern formed thereon. It is not deformed to the extent that it is pressed to assist. Therefore, the ceramic green sheet and the shape of the conductor pattern formed thereon are not deformed, and the obtained ceramic green sheet laminate and the electronic component obtained by firing it have high dimensional accuracy.

  Furthermore, when the melting component of the melting component that melts upon heating has a melting point of 35 ° C. to 100 ° C., the first ceramic green sheet layer does not soften and deform at room temperature. The organic components such as the binder and the plasticizer in the ceramic green sheet are not decomposed during heating, so that delamination does not occur due to the decomposition gas, which is more preferable.

  Further, if the addition amount of the organic binder contained in the first ceramic green sheet layer is 19 to 30 parts by mass with respect to 100 parts by mass of the ceramic powder, the shape retention of the first ceramic green sheet layer is maintained, The first ceramic green sheet layer is softened when the ceramic green sheets on which the conductor layers are formed are laminated and heated, so that the first ceramic green sheet layer is the second ceramic green sheet positioned below the first ceramic green sheet layer. 2 is deformed following the shape of the ceramic green sheet layer and the conductor pattern formed on the ceramic green sheet layer. In addition, it becomes more preferable without delamination or delamination between layers.

  In addition, the addition amount of the organic binder said here is a mass part of the organic binder with respect to 100 mass parts of ceramic powder.

  Further, if the molecular weight of the organic binder contained in the first ceramic green sheet layer is 80,000 to 300,000, the shape retention of the first ceramic green sheet layer is maintained, and the first ceramic green sheet layer When the molten component contained is uniformly dispersed when heated, the ceramic green sheet can be heated to maintain a sufficient amount of the molten component in the first ceramic green sheet layer, and into a ceramic green sheet by pressurization It is more preferable that it can be pressure-bonded with a pressurizing force as low as possible without any distortion, and has small dimensional variations and does not cause delamination or delamination between layers.

  In addition, when the acid value of the organic binder contained in the first ceramic green sheet layer is 0.1 to 0.8 KOH mg / g, the molten component contained in the first ceramic green sheet layer is melted by heating. The ceramic green sheet is uniformly dispersed, and the ceramic green sheet can be heated to maintain a sufficient amount of the melted component of the first ceramic green sheet layer, and is pressed with a low pressure so that the ceramic lean sheet is not distorted by pressurization. It is possible to reduce the dimensional variation and to prevent peeling and delamination between layers.

  Further, when the amount of the organic binder contained in the ceramic slurry to be the second ceramic green sheet layer is 10 to 19 parts by mass with respect to 100 parts by mass of the ceramic powder, the second ceramic green sheet layer is formed. Further, the diffusion amount of the molten component from the first ceramic green sheet layer to the ceramic slurry to be the second ceramic green sheet layer is reduced, and the second ceramic green sheet layer and the conductor formed thereon are laminated at the time of lamination Since a sufficient amount of the low-melting-point component is retained to deform following the shape of the pattern, it is more preferable. Further, when the ceramic slurry is applied on the first ceramic green sheet layer and dried to form the second ceramic green sheet layer to form the ceramic green sheet, the second ceramic green sheet layer becomes brittle. Therefore, the ceramic green sheet is not broken or cracked, which is more preferable.

  In addition, if the molecular weight of the organic binder contained in the ceramic slurry to be the second ceramic green sheet layer is 100,000 to 800,000, the dimensional variation due to the raw deformation of the second ceramic green sheet layer during the processing of the ceramic green sheet And the occurrence of poor appearance such as pinholes in the second ceramic green sheet layer due to non-uniform dispersion of raw material components can be suppressed, which is more preferable.

  In addition, when the acid value of the organic binder contained in the ceramic slurry to be the second ceramic green sheet layer is 0.1 to 5 KOHmg / g, the bond between the inorganic powder and the organic binder is insufficient when the ceramic green sheet is heated. Reduced diffusion of the molten component from the first ceramic green sheet layer to the second ceramic green sheet layer caused by the above, and the appearance of pinholes and the like in the second ceramic green sheet layer due to aggregation of inorganic powders The occurrence of defects can be prevented, which is more preferable.

  In addition, if the glass transition point of the organic binder contained in the first ceramic green sheet layer is −20 to 0 ° C., the shape retaining property of the first ceramic green sheet layer at room temperature can be maintained, so that the lamination step And the first ceramic green sheet layer is easily softened by melting of the molten component during heating when laminating, and the first ceramic green sheet layer and the second ceramic green sheet layer and The shape of the pattern of the conductor layer formed thereon can be made to follow well, and it becomes more preferable without causing delamination and delamination.

  Further, when the hydroxyl value of the organic binder contained in the first ceramic green sheet layer is 0.1 to 5 KOHmg / g, it is uniform when the melting component contained in the first ceramic green sheet layer is melted by heating. Dispersed, since the ceramic green sheet can be heated at the time of lamination to maintain a sufficient amount of the molten component of the first ceramic green sheet layer, it can be pressure-bonded with a low pressure so that there is no distortion to the green sheet due to pressure, The dimensional variation is small, and delamination and delamination do not occur.

  In addition, if the glass transition point of the organic binder contained in the ceramic slurry to be the second ceramic green sheet layer is −20 to 20 ° C., the hard nature of the organic binder appears strongly, so the second ceramic green sheet layer Strengthens and suppresses small dimensional deformation that accompanies the shape of the second ceramic green sheet layer and the conductor pattern formed thereon by softening the first ceramic green sheet layer during heating during lamination Therefore, dimensional variation is small and more preferable.

  In addition, when the hydroxyl value of the organic binder contained in the ceramic slurry to be the second ceramic green sheet layer is 5 to 100 KOHmg / g, the ceramic slurry is attracted by the charge of the hydroxyl group with the charge existing on the surface of the inorganic powder. A solvate is formed in the ceramic green sheet so that the inorganic powder and organic binder contained in the second ceramic green sheet layer are uniformly dispersed and heated during lamination. Since the molten component of the first ceramic green sheet layer can suppress the minute dimensional deformation caused by following the shape of the second ceramic green sheet layer and the conductor pattern formed on the second ceramic green sheet layer, dimensional variation can be suppressed. Smaller and more preferable.

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

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

  The method for manufacturing an electronic component of the present invention will be described in detail below. FIG. 1 is a cross-sectional view for each process showing an example of an embodiment of an electronic component manufacturing method of the present invention. 1 is a support, 2 is a first ceramic green sheet layer, 3 is a ceramic slurry, and 4 is a ceramic. A green sheet, 5 is a conductor layer, and 6 is a ceramic green sheet laminate.

  First, as shown in FIG. 1 (a), a first ceramic green sheet layer 2 is formed on a support 1 made of a PET film, paper or the like whose surface has been released, and then, as shown in FIG. 1 (b). In addition, a ceramic green in which a second ceramic green sheet layer 3 ′ is formed on the first ceramic green sheet layer 2 by applying the ceramic slurry 3 on the first ceramic green sheet layer 2 and drying it. A sheet 4 is formed. At this time, it is important that the difference between the solubility parameter of the first ceramic green sheet layer 2 and the solubility parameter of the ceramic slurry 3 is 3 to 8.

  Since the ceramic green sheet 4 is formed by applying the ceramic slurry 3 on the first ceramic green sheet layer 2, the formation of the second ceramic green sheet layer as the high fluidity layer and the normal ceramic green sheet layer are performed. Since there is no step of drilling a high-fluidity green sheet and step of laminating a high-fluidity green sheet by simultaneously performing lamination on the first ceramic green sheet layer 2, the increase in the number of laminations, It is possible to form a high fluidity layer without causing problems such as longer construction period, higher cost, lower yield, lower reliability of conductor connection between layers, and air entrainment during lamination of high fluidity layer Therefore, it is possible to obtain a highly reliable electronic component without delamination.

  When the ceramic slurry 3 is applied on the first ceramic green sheet layer 2 by setting the difference between the solubility parameter of the first ceramic green sheet layer 2 and the solubility parameter of the ceramic slurry 3 to 3 to 8, Since the first ceramic green sheet layer 2 and the ceramic slurry 3 are prevented from dissolving each other, the first ceramic green sheet layer 2 and the second ceramic green sheet layer 3 ′ are prevented from being mixed and made identical. be able to. In addition, when the ceramic slurry 3 is applied on the first ceramic green sheet layer 2, the ceramic slurry 3 on the first ceramic green sheet layer 2 can be applied without being repelled. Occurrence of delamination can be prevented because there are no voids due to entrainment of bubbles.

  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 parameters of the first ceramic green sheet layer 2 and the ceramic slurry 3 of the present invention were calculated from the solubility parameter of the organic component contained in each and the volume fraction of each organic component. For example, the first ceramic green sheet layer 2 includes two organic components, the solubility parameters are 5 and 7, and the volume fractions are 70% and 30%, respectively. The solubility parameter of layer 2 was 5 × 0.7 + 7 × 0.3 = 5.6. Further, for example, the solubility of the ceramic slurry 3 when the ceramic slurry 3 includes three organic components, the respective solubility parameters are 5, 7, and 9, and the volume fractions are 70%, 20%, and 10%, respectively. The parameters were 5 × 0.7 + 7 × 0.2 + 9 × 0.1 = 5.8. 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.

  The first ceramic green sheet layer 2 and the ceramic slurry 3 in the present invention are a mixture of ceramic powder, an organic binder (binder), a solvent, etc., and the dispersibility of the ceramic powder and the hardness and strength of the ceramic green sheet 4 are used. In order to adjust the viscosity, a dispersant or a plasticizer may be added. When the first ceramic green sheet layer 2 is a high fluidity layer as in the prior art, the first ceramic green sheet layer 2 may contain a larger amount of organic binder or plasticizer than the ceramic slurry 3. Moreover, it is preferable that the 1st ceramic green sheet layer 2 contains the molten component which will be in a molten state at the time of a heating in the process of producing the ceramic green sheet laminated body 6 mentioned later. These organic binders, solvents, plasticizers, and molten components are the 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) And Pb-based glass, Bi-based 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 organic binder, those conventionally used for ceramic green sheets can be used. For example, acrylic (a homopolymer or copolymer of acrylic acid, methacrylic acid or esters thereof, specifically acrylic acid Ester copolymers, methacrylate copolymers, acrylic ester-methacrylic ester copolymers, etc.), polyvinyl butyral, polyvinyl alcohol, acrylic-styrene, polypropylene carbonate, cellulose, etc. A polymer or a copolymer is mentioned. 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 organic 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 first ceramic green sheet layer 2 is in a molten state upon heating when the ceramic green sheet laminate 6 is produced, and is a hydrocarbon, fatty acid, ester, fatty alcohol, polyhydric alcohol. Etc. Considering the solubility in a solvent when preparing the slurry, hydrocarbons, esters, fatty alcohols and polyhydric alcohols having a small molecular weight and polarity are preferred. Further, in view of compatibility with the above-described acrylic binder, esters, fatty alcohols, and polyhydric alcohols are more preferable.

  Among the above-mentioned melting components, those having a melting point of 35 to 100 ° C. are preferable. This is because when the melting point in this range is used, the first ceramic green sheet layer 2 is not softened and deformed at room temperature. This is because organic components such as a binder and a plasticizer in the ceramic green sheet 4 are not decomposed during heating in the production process, and therefore 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 first ceramic green sheet layer 2 varies depending on the binder component to be used and the amount thereof, and the molten component to be used, but the first ceramic green sheet layer is in a melted state. 2 may be an amount that softens and deforms following the shape of the second ceramic green sheet layer 3 ′ of another ceramic green sheet 4 positioned below and the conductor pattern formed thereon. .

  Moreover, it is preferable that the addition amount of the organic binder contained in the 1st ceramic green sheet layer 2 is 19-30 mass% with respect to 100 mass parts of ceramic powder. When the addition amount is lower than 19% by mass, the first ceramic green sheet layer 2 is not sufficiently softened in a state where the molten component is melted. Therefore, the ceramic green sheet 4 formed by applying and drying the ceramic slurry 3 on the first ceramic green sheet layer 2 and the second ceramic green sheet layer 3 of another ceramic green sheet 4 positioned therebelow. 'And it does not change following the shape of the conductor layer 5 formed on it, so that it cannot be crimped with such a low pressure that there is no distortion to the ceramic green sheet 4 due to pressurization, and peeling or delamination between layers Will occur. On the other hand, if the addition amount is higher than 30 parts by mass, the fluidity of the organic binder becomes excessive, the shape retaining property of the first ceramic green sheet layer 2 at room temperature cannot be obtained, and the ceramic green sheet by pressurization Even when crimping with low pressure so that there is no distortion, the laminating dimension deviation is large due to flow, and the decomposition gas of the organic binder at the time of firing is excessive, so the occurrence of bokeh, pinholes, delamination becomes remarkable .

  In addition, the addition amount of the organic binder said here is a mass part of the organic binder with respect to 100 mass parts of ceramic powder.

  The molecular weight of the organic binder contained in the first ceramic green sheet layer 2 is preferably 80,000 to 300,000. When the molecular weight is lower than 80,000, the fluidity of the organic binder at room temperature becomes excessive, the shape retaining property of the first ceramic green sheet layer 2 cannot be obtained, and the green sheet is not distorted by pressurization. Even when pressure bonding is performed at such a low pressure, the laminating dimension shift is large due to flow, and the organic binder of the first ceramic green sheet layer 2 is formed on the second ceramic green sheet layer 3 'and the conductor pattern formed thereon. Therefore, the decomposition gas of the organic binder at the time of firing is excessively generated locally in the ceramic green sheet 4, and the occurrence of bokeh, pinholes and delamination becomes remarkable.

  Moreover, when the said molecular weight exceeds 300,000, organic binder will become easy to get entangled and aggregation will become remarkable. Therefore, the molten component contained in the first ceramic green sheet layer 2 is not uniformly dispersed, and the molten component contained in the first ceramic green sheet layer 2 is not uniformly dispersed when melted by heating, In addition, even when the ceramic green sheet 4 is heated, a sufficient amount of the molten component of the first ceramic green sheet layer 2 cannot be maintained, and the first ceramic green sheet layer 2 is sufficiently softened while the molten component is melted. The ceramic green sheet laminate 6 does not change following the shape of the second ceramic green sheet layer 3 ′ of another ceramic green sheet 4 located below and the conductor layer 5 formed thereon. When forming the film, it cannot be pressure-bonded at such a low pressure that there is no distortion to the green sheet due to pressure, and peeling or delamination between layers Occur.

  The acid value of the organic binder contained in the first ceramic green sheet layer 2 is preferably 0.1 to 0.8 KOHmg / g. When the acid value is lower than 0.1 KOHmg / g, the binding property between the inorganic powder and the organic binder is weakened, and the inorganic powder and the organic binder are aggregated inside the first ceramic green sheet layer 2, respectively. Since it exists in a state, the melted component that is compatible with the organic binder and contained in the first ceramic green sheet layer 2 is not uniformly dispersed. Therefore, even when the ceramic green sheet 4 is heated and the molten component is melted, the first ceramic green sheet layer 2 is not sufficiently softened, and the second ceramic green of another ceramic green sheet 4 positioned therebelow. Since the shape does not change following the shape of the sheet layer 3 ′ and the conductor layer 5 formed thereon, when the ceramic green sheet laminate 6 is formed, a low load is applied so that the green sheet is not distorted by pressure. It cannot be crimped by pressure, and peeling or delamination occurs between layers.

  Moreover, when the said acid value exceeds 0.8 KOHmg / g, the binding property of an organic binder will become strong too much and it will aggregate with organic binders. For this reason, the organic binder and the melted component are hardly compatible, and the melted component contained in the first ceramic green sheet layer 2 is not uniformly dispersed. Therefore, even when the ceramic green sheet 4 is heated and the molten component is melted, the first ceramic green sheet layer 2 is not sufficiently softened, and the second ceramic green sheet of another ceramic green sheet 4 positioned therebelow. Since it does not change following the shape of the layer 3 ′ and the conductor layer 5 formed thereon, when the ceramic green sheet laminate 6 is formed, the applied pressure is low enough that there is no distortion of the green sheet due to pressure. Cannot be crimped, causing delamination or delamination between layers.

  Moreover, it is preferable that the addition amount of the organic binder contained in the ceramic slurry used as the 2nd ceramic green sheet layer 3 is 10-19 mass parts. If the added amount is less than 10 parts by mass, the density of the second ceramic green sheet layer 3 is low, the molten component in the first ceramic green sheet layer 2 is likely to diffuse, and the ceramic is heated during the lamination. The green sheet 4 has an amount of melting component necessary to change following the shape of the second ceramic green sheet layer 3 'of the other ceramic green sheet 4 located below and the conductor layer 5 formed thereon. Can not be maintained, and delamination and delamination occur. Further, since the inorganic powder and the organic binder contained in the second ceramic green sheet layer 3 are not sufficiently bonded, the strength of the second ceramic green sheet layer 3 is weakened, and the ceramic green sheet 4 is broken or cracked. Is likely to occur.

  Moreover, if the said addition amount is more than 19 mass parts, the addition amount of the organic binder contained in the 2nd ceramic green sheet layer 3 will be about the same addition amount as the organic binder contained in the 1st ceramic green sheet layer 2 Therefore, the ceramic green sheet 4 has a second ceramic green sheet layer 3 ′ of another ceramic green sheet 4 positioned under the ceramic green sheet 4 and a conductor layer 5 formed thereon. The amount of molten component necessary to change following the shape cannot be maintained, resulting in delamination and delamination. Furthermore, since the filling rate of the inorganic powder contained in the second ceramic green sheet layer 3 is reduced, a dense sintered body cannot be obtained after firing, and defects such as voids and chips are easily generated in the sintered body. Tend to be.

  The molecular weight of the organic binder contained in the ceramic slurry that becomes the second ceramic green sheet layer 3 is preferably 100,000 to 800,000. When the molecular weight is lower than 100,000, the second ceramic green sheet layer 3 is also deformed with respect to the deformation of the first ceramic green sheet layer 2 at the time of heating at the time of lamination, so that the dimensional variation becomes large. Furthermore, since the opportunities for the organic binders to be entangled with each other are reduced, the viscosity and yield value of the ceramic slurry are excessively lowered, and the ceramic green sheet 4 may be broken by the contact with the heated air in the drying process after slurry application. , Cracks are likely to occur. Furthermore, since the molecular chain becomes longer and the opportunity for the organic binders to be entangled with each other increases, the viscosity and yield value of the ceramic slurry are excessively increased, the leveling property after coating is deteriorated, and the thickness of the ceramic green sheet 4 varies. Tend to be larger. When the molecular weight exceeds 800,000, the binding force between the organic binders becomes strong, and the raw material components contained in the second ceramic green sheet layer 3 are not uniformly dispersed. Appearance defects such as pinholes occur, causing insulation failure in the product.

  Moreover, it is preferable that the acid value of the organic binder contained in the ceramic slurry to be the second ceramic green sheet layer 3 is 0.1 to 5 KOHmg / g. When the acid value is lower than 0.1 KOH mg / g, the bonding property between the inorganic powder and the organic binder becomes weak, and the second ceramic green sheet layer is resistant to deformation of the first ceramic green sheet layer 2 during lamination. 3 is also deformed, resulting in large dimensional variations and poor dispersibility of the inorganic powder and the organic binder in the second ceramic green sheet layer 3, and poor appearance such as pinholes in the second ceramic green sheet layer 3. Will occur. When the acid value exceeds 5 KOHmg / g, the binding between the inorganic powder and the organic binder becomes excessively strong, thereby causing aggregation due to bonding between the inorganic raw materials, and pinning in the second ceramic green sheet layer 3. Appearance defects such as holes occur, causing insulation failure in products.

  Moreover, it is preferable that the glass transition point of the organic binder contained in the 1st ceramic green sheet layer 2 is -20 thru | or 0 degreeC. When the glass transition point is lower than −20 ° C., the soft nature of the organic binder appears strongly at room temperature, and adhesion between the ceramic green sheets 4 occurs. On the other hand, if the glass transition point is higher than 0 ° C., the ceramic green sheet 4 is insufficiently softened due to melting of the molten component at the time of heating, and the ceramic green sheet 4 is separated from another ceramic green. Since it does not change following the shape of the second ceramic green sheet layer 3 ′ of the sheet 4 and the conductor layer 5 formed thereon, the ceramic green sheet 4 by pressurization when the ceramic green sheet laminate 6 is formed. Bonding cannot be performed with such a low pressure that there is no distortion of the film, resulting in delamination and delamination.

  The hydroxyl value of the organic binder contained in the first ceramic green sheet layer 2 is preferably 0.1 to 5 KOHmg / g. When the hydroxyl value is lower than 0.1 KOH mg / g, the bondability between the inorganic powder and the organic binder becomes weak, and the inorganic powder and the organic binder exist in a non-uniform state inside the first ceramic green sheet layer 2. Therefore, the molten component contained in the first ceramic green sheet layer 2 is not uniformly dispersed when melted by heating, and the molten component of the first ceramic green sheet layer 2 is not heated even when the ceramic green sheet 4 is heated. A sufficient amount cannot be maintained, pressure bonding cannot be performed with such a low pressure that the green sheet is not distorted by pressurization, and delamination or delamination occurs. Further, when the hydroxyl value exceeds 5 KOHmg / g, the bondability between the inorganic powder and the binder becomes excessively strong, and the molten component contained in the first ceramic green sheet layer 2 is uniformly dispersed when melted by heating. In other words, the ceramic green sheet 4 cannot be heated to maintain a sufficient amount of the melted component of the first ceramic green sheet layer 2 and cannot be pressed with such a low pressure that the green sheet is not distorted by pressurization. , Delamination and delamination occur.

  Moreover, it is preferable that the glass transition point of the organic binder contained in the ceramic slurry used as the 2nd ceramic green sheet layer 3 is -20 thru | or 20 degreeC. When the glass transition point is lower than −20 ° C., the soft nature of the organic binder appears strongly at room temperature, and adhesion between the ceramic green sheets 4 occurs. On the other hand, if the glass transition point is higher than 20 ° C., the shape retention of the ceramic green sheet 4 is insufficient, and cracks and chips are likely to occur during handling.

  Further, the hydroxyl value of the organic binder contained in the ceramic slurry to be the second ceramic green sheet layer 3 is preferably 5 to 100 KOHmg / g. When the hydroxyl value is lower than 5 KOHmg / g, the bonding property between the inorganic powder and the organic binder becomes weak, and the inorganic powder and the organic binder are present in the second ceramic green sheet layer 3 in a non-uniform state. Therefore, a rough portion of the second ceramic green sheet layer 3 is easily deformed when pressed, and it is difficult to suppress dimensional deformation. Furthermore, delamination is likely to occur between the layers due to the rough portion of the second ceramic green sheet layer 3 of the sintered body. Moreover, when the said hydroxyl value exceeds 100 KOHmg / g, the binding property of an organic binder will become strong too much, and it will couple | bond together with organic binders, without couple | bonding with inorganic powder. Therefore, the inorganic powder and the organic binder are present in a non-uniform state inside the second ceramic green sheet layer 3. Therefore, a rough portion of the second ceramic green sheet layer 3 is easily deformed when pressed, and it is difficult to suppress dimensional deformation. Furthermore, delamination is likely to occur between the layers due to the rough portion of the second ceramic green sheet layer 3 of the sintered body.

  As a method for forming the first ceramic green sheet layer 2 on a support such as a PET film, a known green sheet molding method may be used. After drying by a doctor blade method, a lip coater method, a die coater method or the like, The method of apply | coating and drying the ceramic slurry used as the 1 ceramic green sheet layer 2 is mentioned.

  The application of the ceramic slurry 3 on the first ceramic green sheet layer 2 is performed by cutting or winding up the first ceramic green sheet layer 2 formed on the support 1 to a predetermined size. Then, the ceramic slurry 3 may be applied again and dried, or the ceramic slurry 3 may be applied continuously after forming the first ceramic green sheet layer 2 on the support. The method of applying and drying the ceramic slurry 3 again is not only when the number of steps such as cutting and winding is increased, but also when the ceramic slurry 3 is applied due to damage of the surface of the ceramic green sheet layer 2 or adhesion of foreign matters in this step. Therefore, it is preferable to apply the ceramic slurry 3 continuously.

  Examples of the method for applying the ceramic slurry 3 on the first ceramic green sheet layer 2 include a roll coater method, a doctor blade method, a lip coater method, a die coater method, a slot coater method, and a curtain coater method. Extrusion methods such as a die coater method, a slot coater method and a curtain coater method are preferred. Since these coating methods are non-contact, when the ceramic slurry 3 is formed on the first ceramic green sheet layer 2, the coating head of a coating device such as a die coater, slot coater, curtain coater or the like is used as the first ceramic. The ceramic green sheet 4 may be formed without damaging the green sheet layer 2.

  The thickness of the first ceramic green sheet layer 2 is formed to be thicker than the thickness of the conductor layer in order to fill the step between the conductor layer and the ceramic green sheet.

  Next, as shown in FIG.1 (c), the conductor layer 5 is formed on a ceramic green sheet. As a method of forming the conductor layer 5 on the ceramic green sheet 4, for example, a paste formed from a conductor material powder is printed by a screen printing method or a gravure printing method, or a predetermined pattern shape is formed by a plating method or a vapor deposition method. A method of directly forming on the ceramic green sheet 4 to form a metal film, a conductor thick film formed into a predetermined pattern shape by printing, a metal foil processed into a predetermined pattern shape, a predetermined method formed by a plating method, a vapor deposition method, or the like There is a method of transferring a pattern-shaped metal film onto the ceramic green sheet 4. 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.

  The conductor layer 5 is preferably formed on the second ceramic green sheet layer 3 ′ of the ceramic green sheet 4. This is because the second ceramic green sheet layer 3 ′ does not contain a melting component that melts when heated, and therefore the second ceramic green sheet layer 3 ′ is not deformed when heated, so that the conductor layer 5 is formed thereon. This is to prevent the conductor layer 5 from being deformed by forming.

  In addition, before forming the conductor layer 5, if necessary, a through conductor such as a via-hole conductor or a through-hole conductor for connecting the conductor layers 5 between the upper and lower layers may be formed. These through conductors are formed by a means such as filling and embedding a paste of conductor material powder (conductor paste) by printing or pressing into a through hole formed in the ceramic green sheet 4 by punching or laser processing. .

  In the case of manufacturing an electronic component having a cavity, a cavity-shaped through hole is formed in a part of the ceramic green sheet 4 by punching with a mold or the like before the step of manufacturing the next laminate. The through hole may be formed before or after the conductor layer 5 is formed, depending on whether or not the conductor layer 5 is formed on the inner wall surface of the cavity.

  Next, as shown in FIG.1 (d), the ceramic green sheet laminated body 6 is produced by heat-pressing and crimping | stacking the ceramic green sheet 4 accumulated and aligned. The heating and pressurizing conditions vary depending on the type and amount of the organic binder used, but are generally 30 to 100 ° C. and 2 to 20 MPa. At this time, in order to improve the adhesiveness between the ceramic green sheets 4, an adhesive obtained by mixing a solvent with an organic binder, a plasticizer, or the like may be used.

  When the ceramic slurry to be the first ceramic green sheet 2 includes a melting component, that is, when the first ceramic green sheet layer 2 includes a melting component, the ceramic green sheets 4 that are aligned and stacked are used as the melting component. The ceramic green sheet laminate 6 is produced by heating at a temperature at which the first ceramic green sheet layer 2 is softened and deformed, that is, at a temperature about the melting point of the molten component. Further, at this time, the softened first ceramic green sheet layer 2 is replaced with the second ceramic green sheet layer 3 ′ and the conductor layer 5 formed thereon so that the laminated ceramic green sheets 4 are not displaced. If pressurization (0.1 to 1 MPa) is performed so as to assist in deforming following the pattern shape, more accurate and reliable crimping can be performed.

  In the step of producing the ceramic green sheet laminate 6, the first ceramic green sheet layer 2 contains a melting component that melts when heated, and thus the ceramic green sheet 4 on which the conductor layer 5 is formed is laminated and heated. At this time, the first ceramic green sheet layer 2 is softened, so that the first ceramic green sheet layer 2 is formed on the second ceramic green sheet layer 3 ′ of another ceramic green sheet 4 located thereunder and on the second ceramic green sheet layer 3 ′. The conductor layer 5 is deformed following the shape of the conductor layer 5. As a result, the ceramic green sheets 4 are brought into close contact with each other without generating voids around the conductor layer 5 or between the conductor layers 5, and the electronic component obtained by firing the ceramic green sheet laminate 6 is free from delamination. It will not be.

  In addition, since the first ceramic green sheet layer 2 contains a melting component that melts when heated, the first ceramic green sheet layer 2 is softened and has adhesiveness only by heating. There is no need to press the ceramic green sheet 4 by pressure. Since the second ceramic green sheet layer 3 ′ on which the conductor layer 5 is formed does not contain a melting component that melts when heated, the second ceramic green sheet layer 3 ′ is not deformed when heated, The softened first ceramic green sheet layer 2 follows the shape of the pattern of the second ceramic green sheet layer 3 'and the conductor layer 5 formed thereon so that the ceramic green sheet 4 is not displaced. Thus, it is not deformed to the extent that it is pressed to assist in deformation. Accordingly, the ceramic green sheet 4 and the conductor layer formed thereon are not deformed, and the ceramic green sheet laminate 6 obtained by firing without distortion to the green sheet due to pressurization is obtained. The obtained electronic component has high dimensional accuracy.

  For example, when the first ceramic green sheet layer 2 that does not contain a melting component that melts when heated is used, the dimensional accuracy of the ceramic green sheet laminate 6 and the electronic component is about ± 0.5% (dimensional error). However, when the first ceramic green sheet layer 2 containing the molten component of the present invention is used, the dimensional accuracy of the ceramic green sheet laminate 6 and the electronic component is about ± 0.3%, which can be greatly improved. It became clear by experiment.

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

  As the ceramic green sheet positioned at the bottom of FIG. 1 (d), a ceramic green sheet 4 'composed only of the second ceramic green sheet layer 3' may be used. In the case of an electronic component in which the conductor layer 5 is not exposed on the surface, such as a multilayer capacitor, the ceramic green sheet 4 in which the conductor layer 5 is not formed on the ceramic green sheet 4 positioned at the top of FIG. In the case of an electronic component in which the conductor layer 5 is exposed on both surfaces, such as a multilayer ceramic wiring board, the one in which the conductor layer 5 is formed on both surfaces of the lowermost ceramic green sheet 4 ′ may be used. .

  Finally, the ceramic green sheet laminate 6 is fired to produce the electronic component of the present invention. The firing step consists of removing organic components and sintering the ceramic powder. The organic component is removed by heating the ceramic green sheet laminate 6 in a temperature range of 100 to 800 ° C., the organic component is decomposed and volatilized, and the sintering temperature varies depending on the ceramic composition, and is in the range of about 800 to 1600 ° C. Do it within. 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.

  After firing, the surface of the conductive layer 5 exposed on the surface of the electronic component is provided with a good connection means for preventing corrosion of the conductive layer 5 or for connecting the external substrate such as solder or metal wire or the electronic component. Therefore, Ni or Au plating may be applied.

When a low-temperature sintered material such as glass ceramics is used as the ceramic material, if a constrained green sheet is further laminated on the upper and lower surfaces of the ceramic green sheet laminate 6 and fired, and the restraint sheet is removed after firing, A ceramic substrate with higher dimensional accuracy 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 constraining green sheets are laminated, the constraining green sheet that does not shrink is prevented from shrinking in the laminating plane direction (xy plane direction) and shrinks only in the laminating direction (z direction). Is suppressed. When the constraining green sheet at this time is also configured to have the first ceramic green sheet layer 2 and the second ceramic green sheet layer 3 ′ containing the same melting component as the ceramic green sheet 4 of the present invention, When laminating and crimping, a large pressing force is not required, and the obtained electronic component may have higher dimensional accuracy.

  In addition to the hardly sinterable inorganic component, the constrained green sheet may contain a glass component having a softening point not higher than the firing temperature, for example, the same glass as the glass in the ceramic green sheet 4. This is because the glass softens and bonds with the ceramic green sheet 4 during firing, so that the bond between the ceramic green sheet 4 and the constraining green sheet becomes strong, and a more reliable restraining force can be obtained. When the amount of glass at this time is 0.5 to 15 parts 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 binding green sheet is 0.5%. It is suppressed to the following.

  After firing, the constraining sheet is removed. Examples of the removing 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, a first ceramic slurry obtained by mixing alumina powder, an organic binder, a molten component and isopropyl alcohol as shown in the first ceramic green sheet layer of Table 1 is formed on a PET film by a lip coater method to a thickness of 50 μm. And dried to form a first ceramic green sheet layer. Subsequently, a ceramic slurry prepared by mixing an organic binder and a solvent as shown in the ceramic slurry of Table 1 is applied to the first ceramic green sheet layer at a thickness of 100 μm by a die coater method and dried. A ceramic green sheet was prepared.

In order to confirm whether the first ceramic green sheet layer and the second ceramic green sheet layer were formed in two layers, chromium trioxide was added as a metal pigment to the alumina powder of the first ceramic slurry. In Example 4 and Comparative Example 3 alone, a ceramic green sheet was then laminated and pressed at 80 ° C. and 0.5 MPa to produce a laminate.

  When the cross section of the ceramic green sheet of Example 1 is observed, the green color of chromium trioxide of the metal pigment is thin at the interface between the first ceramic green sheet layer and the second ceramic green sheet layer, and there is a slight diffusion. Although it was seen, it was not diffused to the second ceramic green sheet layer, and two layers were properly formed.

  The cross sections of the ceramic green sheets of Examples 2 to 4 were neither diffused nor separated, and the first ceramic green sheet layer and the second ceramic green sheet layer were formed. Moreover, in the ceramic green sheet of Example 4, the cross section of the laminated body was observed, and it was confirmed that the lamination was possible without delamination.

  On the other hand, in Comparative Example 2 and Comparative Example 3, deformation of the ceramic green sheet was observed when the ceramic slurry was applied on the ceramic green sheet layer. In Comparative Example 1, Comparative Example 2 and Comparative Example 3, the surface of the second ceramic green sheet is colored with chromium trioxide in green, and the first ceramic green sheet layer and the second ceramic green sheet are colored. The layers were mixed and identical.

  Further, in Comparative Example 4, when the ceramic slurry was applied on the ceramic green sheet layer, the ceramic slurry was shed and entrained bubbles. Furthermore, the cross section of the laminate was observed, and peeling and delamination occurred between the ceramic green sheet layers.

  Thus, by setting the difference between the solubility parameter of the first ceramic slurry and the solubility parameter of the second ceramic slurry to 3 to 8, the first ceramic green sheet layer and the second ceramic green sheet layer are mixed. , Can be prevented from being identical. Further, since the ceramic slurry can be applied without being repelled at the time of application, separation and delamination between layers due to entrainment of bubbles can be prevented.

  For the first ceramic green sheet layer, 90 parts by mass of alumina powder and alumina having an average particle diameter of 1 μm as an organic binder, silica, magnesia and calcia as sintering aids, and transition metal oxides as color pigments (trioxide) (Chromium) and 100 parts by mass of ceramic powder prepared at a ratio of 10 parts by mass, methyl methacrylate resin was prepared at 18, 19, 20, 25, 30, 32, and 35 parts by mass, respectively. As a solid slurry, 10 parts by mass of hexadecanol was mixed with a ball mill using toluene and ethyl acetate as solvents to prepare a ceramic slurry.

  Next, the ceramic slurry for the first ceramic green sheet layer was applied on a PET film at a thickness of 50 μm by a lip coater method and dried to form a first ceramic green sheet layer.

  Subsequently, 10 parts by mass of a solid content of 100 parts by mass of a methyl methacrylate resin as a ceramic powder and 100 parts by mass of the ceramic powder prepared as a ceramic slurry for the first ceramic green sheet layer and an organic binder, and a plasticizer 1 part by weight of dibutyl phthalate is added, and a ceramic slurry is prepared by mixing with toluene and ethyl acetate as a solvent by a ball mill, and thickened by a die coater method on the previously formed first ceramic green sheet layer. A ceramic green sheet was prepared by coating at a thickness of 100 μm and drying.

  On the second ceramic green sheet layer of this ceramic green sheet, a conductor paste containing tungsten as a main component was printed in a predetermined pattern with a thickness of 10 to 20 μm by screen printing to form a conductor layer.

  Four ceramic green sheets on which conductor layers were formed were superposed and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce a ceramic green sheet laminate. The peel strength at that time is determined by observing the peeling occurrence position when peeling any ceramic green sheet of the ceramic green sheet laminate between the layers with a binocular microscope, and the peeling place is in the second ceramic green sheet. It was a good product.

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

The cross section of this sintered body was observed, and the delamination between the ceramic layers was investigated. Table 2 shows the evaluation results according to the amount of the organic binder contained in the first ceramic slurry.

  In Table 2, the shape retention column of the first ceramic green sheet layer is “◯”. After forming the first ceramic green sheet layer, 5 sheets are stacked and allowed to stand at room temperature for 24 hours. It shows that the first ceramic green sheet layers of each other did not stick together and maintained shape retention. “△” indicates that the first ceramic green sheet layer was formed, but when the five sheets were stacked and left at room temperature for 24 hours after forming, the first ceramic green sheet layers adhered to each other, and the shape retention was continued. Indicates that sex could not be maintained. Further, “◯” in the column of peel strength indicates that the peeled portion was in the second ceramic green sheet layer when the ceramic green sheet laminate was peeled off. “Δ” indicates that the peeled portion was outside the second ceramic green sheet layer. Further, “◯” in the column of the lamination dimension indicates that the dimension after lamination was measured with a three-dimensional measuring machine, and the dimensional variation was smaller than ± 0.05%. “Δ” indicates that although there was no problem in the product dimensions, the dimensional variation was ± 0.05% or more. In addition, “◯” in the column of the presence / absence of inner layer delamination indicates that no delamination was observed inside the sintered body, which was excellent. “Δ” indicates that although there was no problem in the formation of the ceramic green sheet laminate, delamination was observed inside the sintered body. In addition, “◯” in the column of presence / absence of buku / pinhole indicates that there is no buku or pinhole inside the sintered body. “Δ” indicates that although there was no problem in the formation of the ceramic green sheet laminate, burr and pinholes were observed inside the sintered body.

  From Table 2, the sample No. 1 in which the amount of the organic binder added to the first ceramic green sheet layer is less than 19 parts by mass. In No. 1, the peeled portion was outside the second ceramic green sheet layer, and delamination occurred inside the sintered body.

  In addition, sample No. in which the addition amount is larger than 30 parts by mass. Nos. 6 and 7 cannot retain the shape retention of the first ceramic green sheet layer, and the dimensional variation of the laminated dimension is ± 0.05% or more, and delamination, buku / pinhole in the sintered body It was observed.

  On the other hand, sample No. with the above addition amount of 19 to 30 parts by mass. 2, 3, 4, and 5, the shape retention of the first ceramic green sheet layer is obtained, and the peeled portion is within the second ceramic green sheet layer, and the dimensional variation of the lamination dimension is from ± 0.05% However, there was no delamination inside the sintered body, and no buku / pinholes were observed.

  As in Example 2, for the first ceramic green sheet layer, 90 parts by mass of alumina powder and alumina having an average particle diameter of 1 μm as an organic binder, silica, magnesia, calcia as a sintering aid, and transition as a color pigment Based on 100 parts by mass of ceramic powder prepared by combining 10 parts by mass with a metal oxide (chromium trioxide), 20 parts by mass of methyl methacrylate resin in solid content and 4 molecular weight of methyl methacrylate resin. 10, 80,000, 200,000, 300,000, 360,000 and 500,000, respectively, 10 parts by mass of hexadecanol as a low melting point component in a solid content, 40 hours by ball mill using toluene and ethyl acetate as solvents Mixed to prepare a ceramic slurry.

  Next, the ceramic slurry for the first ceramic green sheet layer was applied on a PET film at a thickness of 50 μm by a lip coater method and dried to form a first ceramic green sheet layer.

  Subsequently, as a plasticizer, 10 parts by weight of a solid content of methyl methacrylate resin as a ceramic powder and 100 parts by weight of ceramic powder as an organic binder prepared in the same proportion as the ceramic slurry for the first ceramic green sheet layer 1 part by weight of dibutyl phthalate is added, and a ceramic slurry is prepared by mixing with toluene and ethyl acetate as a solvent by a ball mill, and the thickness is formed on the previously formed first ceramic green sheet layer by a die coater method. A ceramic green sheet was prepared by coating at 100 μm and drying.

  On the second ceramic green sheet layer of this ceramic green sheet, a conductor paste containing tungsten as a main component was printed in a predetermined pattern with a thickness of 10 to 20 μm by screen printing to form a conductor layer.

  Four ceramic green sheets on which conductor layers were formed were superposed and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce a ceramic green sheet laminate.

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

The cross section of this sintered body was observed, and the delamination between the ceramic layers was investigated. Table 3 shows the evaluation results for each molecular weight of the organic binder contained in the first ceramic slurry.

  In Table 3, in the column of shape retention of the first ceramic green sheet layer, “◯” indicates that, after forming the first ceramic green sheet layer, 5 sheets are stacked and allowed to stand at room temperature for 24 hours. It shows that the first ceramic green sheet layers of each other did not stick together and maintained shape retention. “△” indicates that the first ceramic green sheet layer was formed, but after forming the first ceramic green sheet layer 5 layers and left at room temperature for 24 hours, the first ceramic green sheet layers stick to each other. This indicates that the shape retention could not be maintained. Further, “◯” in the column of peel strength indicates that the peeled portion was in the second ceramic green sheet when the ceramic green sheet laminate was peeled off. “Δ” indicates that the peeled portion was outside the second ceramic green sheet layer. Further, “◯” in the column of the lamination dimension indicates that the dimension after lamination was measured with a three-dimensional measuring machine, and the dimensional variation was smaller than ± 0.05%. “Δ” indicates that although there was no problem in the product dimensions, the dimensional variation was ± 0.05% or more. In addition, “◯” in the column of the presence / absence of inner layer delamination indicates that no delamination was observed inside the sintered body, which was excellent. “Δ” indicates that although there was no problem in the formation of the ceramic green sheet laminate, delamination was observed inside the sintered body. In addition, “◯” in the column of presence / absence of buku / pinhole indicates that there is no buku or pinhole inside the sintered body. “Δ” indicates that although there was no problem in the formation of the ceramic green sheet laminate, burr and pinholes were observed inside the sintered body.

  From Table 3, the sample No. with a molecular weight of the organic binder contained in the first ceramic green sheet layer of less than 80,000 was obtained. In No. 1, the shape retention of the first ceramic green sheet layer was not obtained, delamination and bokeh / pinholes were observed inside the sintered body, and the dimensional variation of the lamination dimensions was ± 0.05% or more. It was.

  In addition, the sample No. In Nos. 6 and 7, the peeled portion was outside the second ceramic green sheet layer, and delamination occurred inside the sintered body.

  On the other hand, sample Nos. With a molecular weight of 80,000 to 300,000 are used. 2, 3, 4, and 5, the shape-retaining property of the first ceramic green sheet layer is obtained, and the peeled portion is within the second ceramic green sheet layer, and the dimensional variation of the lamination dimension is more than ± 0.05%. It was small, there was no delamination inside the sintered body, and no buku / pinholes were seen.

  As in Example 3, for the first ceramic green sheet layer, 90 parts by mass of alumina powder and alumina having an average particle size of 1 μm as an organic binder, silica, magnesia, calcia as a sintering aid, and transition as a color pigment To 100 parts by mass of ceramic powder prepared by combining 10 parts by mass with a metal oxide (chromium trioxide), 20 parts by mass of methyl methacrylate resin in solid content of organic binder of methyl methacrylate resin The acid values were respectively prepared at 0.0, 0.1, 0.5, 0.8, 0.9, and 1.5 KOH mg / g, and 10 parts by mass of hexadecanol as a low melting point component, A ceramic slurry was prepared by mixing for 40 hours with a ball mill using ethyl acetate as a solvent.

  Next, the ceramic slurry for the first ceramic green sheet layer was applied on a PET film at a thickness of 50 μm by a lip coater method and dried to form a first ceramic green sheet layer.

  Subsequently, as a plasticizer, 10 parts by weight of a solid content of methyl methacrylate resin as a ceramic powder and 100 parts by weight of ceramic powder as an organic binder prepared in the same proportion as the ceramic slurry for the first ceramic green sheet layer 1 part by weight of dibutyl phthalate is added, and a ceramic slurry is prepared by mixing with toluene and ethyl acetate as a solvent by a ball mill, and the thickness is formed on the previously formed first ceramic green sheet layer by a die coater method. A ceramic green sheet was prepared by coating at 100 μm and drying.

  On the second ceramic green sheet layer of this ceramic green sheet, a conductor paste containing tungsten as a main component was printed in a predetermined pattern with a thickness of 10 to 20 μm by screen printing to form a conductor layer.

  Four ceramic green sheets on which conductor layers were formed were superposed and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce a ceramic green sheet laminate.

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

The cross section of the sintered body was observed, and the presence or absence of delamination between the ceramic layers and the occurrence of bumps or pinholes and the product dimensions were investigated. Table 4 shows the evaluation results by acid value of the organic binder contained in the first ceramic slurry.

  In Table 4, “◯” in the peel strength column indicates that the peeled portion was in the second ceramic green sheet layer when the ceramic green sheet laminate was peeled. “Δ” indicates that it was out of the second ceramic green sheet layer. Further, “◯” in the column of the lamination dimension indicates that the dimension after lamination was measured with a three-dimensional measuring machine, and the dimensional variation was smaller than ± 0.05%. “Δ” indicates that although there was no problem in the product dimensions, the dimensional variation was ± 0.05% or more. In addition, “◯” in the column of the presence / absence of inner layer delamination indicates that no delamination was observed inside the sintered body, which was excellent. “Δ” indicates that although there was no problem in the formation of the ceramic green sheet laminate, delamination was observed inside the sintered body.

  From Table 4, sample No. whose acid value of the organic binder contained in the first ceramic green sheet layer is less than 0.1 KOHmg / g. In No. 1, the peeled portion was outside the second ceramic green sheet layer, the dimensional variation of the lamination dimension was ± 0.05% or more, and delamination occurred inside the sintered body.

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

  On the other hand, Sample No. with the acid value of 0.1 to 0.8 KOHmg / g. In Nos. 2, 3 and 4, the peeled portion was in the second ceramic green sheet layer, the dimensional variation of the lamination dimension was less than ± 0.05%, and there was no delamination inside the sintered body.

  For the first ceramic green sheet layer, 90 parts by mass of alumina powder and alumina having an average particle diameter of 1 μm as an organic binder, silica, magnesia and calcia as sintering aids, and transition metal oxides as color pigments (trioxide) Chromium) and 100 parts by mass of ceramic powder prepared at a rate of 10 parts by mass, 20 parts by mass of methyl methacrylate resin is prepared, and 10 parts by mass of hexadecanol as a melting component in toluene, toluene. The mixture was mixed with a ball mill using ethyl acetate as a solvent to prepare a ceramic slurry.

  Next, this ceramic slurry was applied to a PET film with a thickness of 50 μm by a lip coater method and dried to form a first ceramic green sheet layer.

  Subsequently, the ceramic powder prepared in the same proportion as the ceramic slurry for the first ceramic green sheet layer and methyl methacrylate resin as an organic binder were used in solid content of 8, 9, 10, 12, 15, 17, 19, 20, and 21 parts by mass of each, 1 part by mass of dibutyl phthalate as a plasticizer, and mixing by a ball mill using toluene and ethyl acetate as a solvent, the second ceramic green sheet layer A ceramic slurry was prepared, applied to the first ceramic green sheet layer previously formed at a thickness of 100 μm by the die coater method, and dried to prepare a ceramic green sheet.

  On the second ceramic green sheet layer of this ceramic green sheet, a conductor paste containing tungsten as a main component was printed in a predetermined pattern with a thickness of 10 to 20 μm by screen printing to form a conductor layer. Four ceramic green sheets on which conductor layers were formed were superposed and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce a ceramic green sheet laminate. The peel strength at that time is determined by observing the peeling occurrence position when peeling any ceramic green sheet of the ceramic green sheet laminate between the layers with a binocular microscope, and the peeling place is in the second ceramic green sheet. It was a good product.

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

The cross section (cross section) of this sintered body was observed, and the delamination between the ceramic layers was investigated. And the evaluation result according to the amount of organic binders contained in the first ceramic slurry is shown in Table 5.

  In the peel strength column in Table 5, “◯” indicates that the peeled portion was in the second ceramic green sheet layer when the ceramic green sheet laminate was peeled. “Δ” indicates that it was out of the second ceramic green sheet layer. In addition, “◯” in the column of the presence / absence of inner layer delamination indicates that no delamination was observed inside the sintered body, which was excellent. “Δ” indicates that although there was no problem in the formation of the ceramic green sheet laminate, delamination was observed inside the sintered body. In the sheet appearance column, “◯” indicates that the ceramic green sheet was torn and no cracks were generated when the ceramic green sheet was molded. On the other hand, “Δ” indicates that a portion of the ceramic green sheet was torn and cracks were observed.

  From the results shown in Table 5, the sample No. 1 with an organic binder added in the ceramic slurry to be the second ceramic green sheet layer is less than 10 parts by mass. In Nos. 1 and 2, the peeled portion was outside the second ceramic green sheet layer, delamination was generated inside the sintered body, and cracks were confirmed on the surface of the ceramic green sheet after molding the ceramic green sheet.

  In addition, Sample No. in which the addition amount is larger than 19 parts by mass. Similarly, in 8 and 9, the peeled portion was outside the second ceramic green sheet layer, and delamination occurred inside the sintered body.

  On the other hand, sample Nos. 10 to 19 parts by mass are added. In Nos. 3 to 7, the peeled portion was in the second ceramic green sheet and there was no delamination, and the appearance of the ceramic green sheet was excellent and excellent.

  For the first ceramic green sheet layer, 90 parts by mass of alumina powder and alumina having an average particle diameter of 1 μm as an organic binder, silica, magnesia and calcia as sintering aids, and transition metal oxides as color pigments (trioxide) Chromium) and 100 parts by mass of ceramic powder prepared at a rate of 10 parts by mass, 20 parts by mass of methyl methacrylate resin is prepared, and 10 parts by mass of hexadecanol as a melting component in toluene, toluene. The mixture was mixed with a ball mill using ethyl acetate as a solvent to prepare a ceramic slurry.

  Next, this ceramic slurry was applied to a PET film with a thickness of 50 μm by a lip coater method and dried to form a first ceramic green sheet layer.

  Subsequently, a ceramic powder prepared in the same ratio as the ceramic slurry for the first ceramic green sheet layer and a methyl methacrylate resin as an organic binder were added in an amount of 10 parts by mass with respect to 100 parts by mass of the ceramic powder. The molecular weights of this methyl methacrylate resin were respectively prepared at 80,000, 100,000, 200,000, 300,000, 500,000, 700,000, 800,000, 850,000, and 900,000. Further, 1 part by mass of dibutyl phthalate as a plasticizer was added, and a ceramic slurry to be a second ceramic green sheet layer was prepared by mixing with toluene and ethyl acetate as a solvent by a ball mill, A ceramic green sheet was prepared by coating the ceramic green sheet layer of 1 with a thickness of 100 μm by a die coater method and drying.

  On the second ceramic green sheet layer of this ceramic green sheet, a conductor paste containing tungsten as a main component was printed in a predetermined pattern with a thickness of 10 to 20 μm by screen printing to form a conductor layer. Four ceramic green sheets on which conductor layers were formed were superposed and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce a ceramic green sheet laminate. The peel strength at that time is determined by observing the peeling occurrence position when peeling any ceramic green sheet of the ceramic green sheet laminate between the layers with a binocular microscope, and the peeling place is in the second ceramic green sheet. It was a good product.

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

The cross section of this sintered body was observed, and the delamination between the ceramic layers was investigated. Table 6 shows the evaluation results according to the amount of the organic binder contained in the first ceramic slurry.

  In the column of presence / absence of inner layer delamination in Table 6, “◯” indicates that no delamination was observed inside the sintered body, which was excellent. “Δ” indicates that although there was no problem in the formation of the ceramic green sheet laminate, delamination was observed inside the sintered body. Further, “◯” in the column of the lamination dimension indicates that the dimension after lamination was measured with a three-dimensional measuring machine, and the dimensional variation was smaller than ± 0.05%. “Δ” indicates that although there was no problem in the product dimensions, the dimensional variation was ± 0.05% or more. In the sheet appearance column, “◯” indicates that the ceramic green sheet was torn and no cracks were generated when the ceramic green sheet was molded. On the other hand, “Δ” indicates that a portion of the ceramic green sheet was torn and cracks were observed. In the thickness variation column of the ceramic green sheet, “◯” indicates that 3σ (three times the standard deviation) is within 5% of the average thickness, while “Δ” indicates that it is 5% or more.

  From the results shown in Table 3, the sample No. 1 with a molecular weight of the organic binder contained in the ceramic slurry to be the second ceramic green sheet layer is less than 100,000. In No. 1, delamination occurred in the sintered body, and the dimensional variation in the lamination dimension was 0.05% or more. Moreover, the crack was confirmed on the ceramic green sheet surface after ceramic green sheet molding.

  Sample Nos. With molecular weights greater than 800,000 were used. In Nos. 8 and 9, delamination occurs in the sintered body, the dimensional variation of the lamination dimension is 0.05% or more, and the thickness variation of the ceramic green sheet is 3σ (three times the standard deviation). Of 5% or more.

  On the other hand, sample Nos. With a molecular weight of 100,000 to 800,000 are used. In Nos. 2 to 7, there was no inner layer delamination, and the dimensional variation and the ceramic green sheet thickness variation were excellent.

  For the first ceramic green sheet layer, 90 parts by mass of alumina powder and alumina having an average particle diameter of 1 μm as an organic binder, silica, magnesia and calcia as sintering aids, and transition metal oxides as color pigments (trioxide) Chromium) and 100 parts by mass of ceramic powder prepared at a rate of 10 parts by mass, 20 parts by mass of methyl methacrylate resin is prepared, and 10 parts by mass of hexadecanol as a melting component in toluene, toluene. The mixture was mixed with a ball mill using ethyl acetate as a solvent to prepare a ceramic slurry.

  Next, this ceramic slurry was applied to a PET film with a thickness of 50 μm by a lip coater method and dried to form a first ceramic green sheet layer.

  Subsequently, 10 parts by mass of solid powder with respect to 100 parts by mass of the ceramic powder and methyl methacrylate resin as an organic binder prepared in the same proportion as the ceramic slurry for the first ceramic green sheet layer, The acid value of this methyl methacrylate resin was prepared at 0, 0.1, 2.5, 4, 5, 5.5 KOHmg / g, respectively. Further, 1 part by mass of dibutyl phthalate as a plasticizer was added, and a ceramic slurry to be a second ceramic green sheet layer was prepared by mixing with toluene and ethyl acetate as a solvent by a ball mill, A ceramic green sheet was prepared by coating the ceramic green sheet layer of 1 with a thickness of 100 μm by a die coater method and drying.

  On the second ceramic green sheet layer of this ceramic green sheet, a conductor paste containing tungsten as a main component was printed in a predetermined pattern with a thickness of 10 to 20 μm by screen printing to form a conductor layer. Four ceramic green sheets on which conductor layers were formed were superposed and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce a ceramic green sheet laminate. The peel strength at that time is determined by observing the peeling occurrence position when peeling any ceramic green sheet of the ceramic green sheet laminate between the layers with a binocular microscope, and the peeling place is in the second ceramic green sheet. It was a good product.

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

The cross section of this sintered body was observed, and the delamination between the ceramic layers was investigated. Table 7 shows the evaluation results according to the amount of the organic binder contained in the first ceramic slurry.

  The column “◯” in the presence / absence of inner layer delamination in Table 7 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 ceramic green sheet laminate, delamination was observed inside the sintered body. Further, “◯” in the column of the lamination dimension indicates that the dimension after lamination was measured with a three-dimensional measuring machine, and the dimensional variation was smaller than ± 0.05%. “Δ” indicates that although there was no problem in the product dimensions, the dimensional variation was ± 0.05% or more.

  From the results shown in Table 7, the sample number of the organic binder contained in the ceramic slurry that becomes the second ceramic green sheet layer 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. whose acid value is larger than 5 KOHmg / g. In No. 6, delamination occurred inside the sintered body, and the dimensional variation in the lamination dimension was 0.05% or more.

  On the other hand, Sample No. with the acid value of 0.1 to 5 KOHmg / g. Nos. 2 to 5 had no inner layer delamination and were excellent in dimensional variation.

  For the first ceramic green sheet layer, 90 parts by mass of alumina powder and alumina having an average particle diameter of 1 μm as an organic binder, silica, magnesia and calcia as sintering aids, and transition metal oxides as color pigments (trioxide) Chrome) and 100 parts by mass of ceramic powder prepared at a ratio of 10 parts by mass, 20 parts by mass of methyl methacrylate resin in solid content, and the glass transition point of the organic binder of methyl methacrylate resin is -25, Ceramic slurry prepared by mixing at -20, -10, -5, 0, 5, 10 ° C, 10 parts by mass of hexadecanol as a melting component, and 40 and 40 hours by ball mill using toluene and ethyl acetate as solvents. Was prepared.

  Next, this ceramic slurry was applied to a PET film with a thickness of 50 μm by a lip coater method and dried to form a first ceramic green sheet layer.

  Subsequently, the ceramic powder prepared in the same proportion as the ceramic slurry for the first ceramic green sheet layer and methyl methacrylate resin as an organic binder, 10 parts by mass in solid content with respect to 100 parts by mass of the ceramic powder, plasticizer 1 part by weight of dibutyl phthalate is added, and a ceramic slurry is prepared by mixing with toluene and ethyl acetate as a solvent by a ball mill, and thickened by a die coater method on the previously formed first ceramic green sheet layer. A ceramic green sheet was prepared by coating at a thickness of 100 μm and drying.

  On the second ceramic green sheet layer of this ceramic green sheet, a conductor paste containing tungsten as a main component was printed in a predetermined pattern with a thickness of 10 to 20 μm by screen printing to form a conductor layer. Four ceramic green sheets on which conductor layers were formed were superposed and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce a ceramic green sheet laminate.

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

The cross section of the sintered body was observed, and the presence or absence of delamination between the ceramic layers and the product dimensions were investigated. Table 8 shows the evaluation results for each glass transition point of the organic binder contained in the first ceramic green sheet layer.

  In Table 8, in the column of the shape retention of the first ceramic green sheet layer, “◯” indicates that, after forming the first ceramic green sheet layer, 5 sheets are stacked and allowed to stand at room temperature for 24 hours. It shows that the first ceramic green sheet layers of each other maintained shape retention without sticking. “△” indicates that the first ceramic green sheet layer was formed, but after forming the first ceramic green sheet layer, if the first ceramic green sheet layer is stacked and left at room temperature for 24 hours, the first ceramic green sheet layers stick to each other. This indicates that the shape retention could not be maintained. Further, “◯” in the column of peel strength indicates that the peeled portion was in the second ceramic green sheet layer when the ceramic green sheet laminate was peeled off. “Δ” indicates that it was out of the second ceramic green sheet layer. Further, “◯” in the column of the lamination dimension indicates that the dimension after lamination was measured with a three-dimensional measuring machine, and the dimensional variation was smaller than ± 0.05%. “Δ” indicates that although there was no problem in the product dimensions, the dimensional variation was ± 0.05% or more. In addition, “◯” in the column of the presence / absence of inner layer delamination indicates that no delamination was observed inside the sintered body, which was excellent. “Δ” indicates that although there was no problem in the formation of the laminate, delamination was observed inside the sintered body.

  From Table 8, the sample No. 2 in which the glass transition point of the organic binder contained in the first ceramic green sheet layer is lower than −20 ° C. In No. 1, the shape retention of the first ceramic green sheet layer could not be maintained, and the dimensional variation of the lamination dimension was 0.05% or more.

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

  On the other hand, sample Nos. With glass transition points of 0 to -20 ° C. 2 to 5, the shape-retaining property of the first ceramic green sheet layer is obtained, the peeled portion is in the second ceramic green sheet layer, and the dimensional variation of the lamination dimension is smaller than ± 0.05%, There was no delamination inside the sintered body.

  For the first ceramic green sheet layer, 90 parts by mass of alumina powder and alumina having an average particle diameter of 1 μm as an organic binder, silica, magnesia and calcia as sintering aids, and transition metal oxides as color pigments (trioxide) And 100) by weight of ceramic powder prepared at a ratio of 10 parts by mass with 20 parts by mass of methyl methacrylate resin in solid content, and the hydroxyl value of the organic binder of methyl methacrylate resin is 0.0. Prepared at 1,1,3,4,5,5.5,6KOHmg / g, respectively, 10 parts by mass of hexadecanol as a low melting point component in solids, and mixed for 40 hours with a ball mill using toluene and ethyl acetate as solvents. A ceramic slurry was prepared.

  Next, this ceramic slurry was applied to a PET film with a thickness of 50 μm by a lip coater method and dried to form a first ceramic green sheet layer.

  Subsequently, the ceramic powder prepared in the same proportion as the ceramic slurry for the first ceramic green sheet layer and methyl methacrylate resin as an organic binder, 10 parts by mass in solid content with respect to 100 parts by mass of the ceramic powder, plasticizer 1 part by weight of dibutyl phthalate is added, and a ceramic slurry is prepared by mixing with toluene and ethyl acetate as a solvent by a ball mill, and thickened by a die coater method on the previously formed first ceramic green sheet layer. A ceramic green sheet was prepared by coating at a thickness of 100 μm and drying.

  On the second ceramic green sheet layer of this ceramic green sheet, a conductor paste containing tungsten as a main component was printed in a predetermined pattern with a thickness of 10 to 20 μm by screen printing to form a conductor layer. Four ceramic green sheets on which conductor layers were formed were superposed and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce a ceramic green sheet laminate.

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

The cross section of the sintered body was observed, and the presence or absence of delamination between the ceramic layers and the product dimensions were investigated. Table 9 shows the evaluation results by hydroxyl value of the organic binder of the first ceramic green sheet.

  In the peel strength column in Table 9, “◯” indicates that the peeled portion was in the second ceramic green sheet layer when the ceramic green sheet laminate was peeled. “Δ” indicates that it was out of the second ceramic green sheet layer. Further, “◯” in the column of the lamination dimension indicates that the dimension after lamination was measured with a three-dimensional measuring machine, and the dimensional variation was smaller than ± 0.05%. “Δ” indicates that although there was no problem in the product dimensions, the dimensional variation was ± 0.05% or more. In addition, “◯” in the column of the presence / absence of interlayer delamination indicates that no delamination was observed inside the sintered body, which was excellent. “Δ” indicates that although there was no problem in the formation of the laminate, delamination was observed inside the sintered body.

  From Table 9, sample No. with a hydroxyl value of the organic binder contained in the first ceramic green sheet layer of less than 0.1 KOHmg / g. In No. 1, the peeled portion was outside the second ceramic green sheet layer, the dimensional variation of the lamination dimension was ± 0.05% or more, and delamination occurred inside the sintered body.

  In addition, Sample No. whose hydroxyl value was larger than 5 KOHmg / g. In Nos. 7 and 8, the peeled portion was outside the second ceramic green sheet layer, the dimensional variation of the lamination dimension was ± 0.05% or more, and delamination occurred inside the sintered body.

  On the other hand, Sample No. with the hydroxyl value of 0.1 to 5 KOHmg / g. In Nos. 2 to 6, the peeled portion was in the second ceramic green sheet layer, the dimensional variation in the lamination dimension was less than ± 0.05%, and there was no delamination inside the sintered body.

  For the first ceramic green sheet layer, 90 parts by mass of alumina powder and alumina having an average particle diameter of 1 μm as an organic binder, silica, magnesia and calcia as sintering aids, and transition metal oxides as color pigments (trioxide) Chromium) and 100 parts by mass of ceramic powder prepared at a rate of 10 parts by mass, 20 parts by mass of methyl methacrylate resin is prepared, and 10 parts by mass of hexadecanol as a melting component in toluene, toluene. The mixture was mixed with a ball mill using ethyl acetate as a solvent to prepare a ceramic slurry.

  Next, this ceramic slurry was applied to a PET film with a thickness of 50 μm by a lip coater method and dried to form a first ceramic green sheet layer.

  Subsequently, 10 parts by mass of solid powder with respect to 100 parts by mass of the ceramic powder and methyl methacrylate resin as an organic binder prepared in the same proportion as the ceramic slurry for the first ceramic green sheet layer, The glass transition point of this methyl methacrylate resin was prepared at −22, −20, 0, 10, 20, and 25 ° C., respectively. Further, 1 part by mass of dibutyl phthalate as a plasticizer was added, and a ceramic slurry to be a second ceramic green sheet layer was prepared by mixing with toluene and ethyl acetate as a solvent by a ball mill, A ceramic green sheet was prepared by coating the ceramic green sheet layer of 1 with a thickness of 100 μm by a die coater method and drying.

Using this ceramic green sheet, the adhesion between ceramic green sheets when handling at room temperature and the cracking chipping of the sheet were evaluated. Table 10 shows the evaluation results for each glass transition point of the organic binder contained in the second ceramic green sheet layer.

  In the sheet adhesion column in Table 10, “◯” indicates that the ceramic green sheets did not adhere to each other and were easy to handle when the ceramic green sheets were handled at room temperature. On the other hand, “Δ” indicates that the ceramic green sheets are adhered to each other only when they are stacked at room temperature and are difficult to handle. In the sheet crack and chip column, “◯” indicates that the ceramic green sheet was easy to handle without cracking or chipping when handled at room temperature. On the other hand, “Δ” indicates that the ceramic green sheet was cracked or chipped when handled at room temperature and was difficult to handle.

  From Table 2, the sample No. whose glass transition point of the organic binder contained in the ceramic slurry used as the 2nd ceramic green sheet layer is less than -20 degreeC is shown. In No. 1, sheet adhesion occurred.

  Sample No. with a glass transition point higher than 20 ° C. was used. In No. 6, sheet cracking or chipping occurred.

  On the other hand, sample Nos. With a glass transition point of −200,000 to 20 were used. In Nos. 2 to 5, there was no sheet adhesion, and no sheet cracking or adhesion occurred.

  For the first ceramic green sheet layer, 90 parts by mass of alumina powder and alumina having an average particle diameter of 1 μm as an organic binder, silica, magnesia and calcia as sintering aids, and transition metal oxides as color pigments (trioxide) Chromium) and 100 parts by mass of ceramic powder prepared at a rate of 10 parts by mass, 20 parts by mass of methyl methacrylate resin is prepared, and 10 parts by mass of hexadecanol as a melting component in toluene, toluene. The mixture was mixed with a ball mill using ethyl acetate as a solvent to prepare a ceramic slurry.

  Next, this ceramic slurry was applied to a PET film with a thickness of 50 μm by a lip coater method and dried to form a first ceramic green sheet layer.

  Subsequently, 10 parts by mass of solid powder with respect to 100 parts by mass of the ceramic powder and methyl methacrylate resin as an organic binder prepared in the same proportion as the ceramic slurry for the first ceramic green sheet layer, The hydroxyl value of this methyl methacrylate resin was prepared at 0, 3, 5, 10, 20, 40, 60, 80, 100, 104, and 110 KOH mg / g, respectively. Further, 1 part by mass of dibutyl phthalate as a plasticizer was added, and a ceramic slurry to be a second ceramic green sheet layer was prepared by mixing with toluene and ethyl acetate as a solvent by a ball mill, A ceramic green sheet was prepared by coating the ceramic green sheet layer of 1 with a thickness of 100 μm by a die coater method and drying.

  On the second ceramic green sheet layer of the ceramic sheet, a conductor paste containing tungsten as a main component was printed in a predetermined pattern with a thickness of 10 to 20 μm by screen printing to form a conductor layer. Four ceramic green sheets on which conductor layers were formed were superposed and thermocompression bonded at a pressure of 0.5 MPa and a temperature of 80 ° C. in the thickness direction to produce a ceramic green sheet laminate.

In order to remove organic components such as an organic binder in the ceramic green sheet laminate and carbon remaining after the organic components are decomposed, the temperature is 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, a ceramic sintered body for evaluation was produced by holding at a temperature of about 1600 ° C. for 1 hour in a reducing atmosphere.

The sintered body was cross-sectioned, and the presence or absence of delamination between the ceramic layers and the product dimensions were investigated. And the result of evaluation according to the hydroxyl value of the organic binder contained in the second ceramic green sheet layer is shown in Table 11.

  The column “◯” in the presence / absence of inner layer delamination in Table 11 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 ceramic green sheet laminate, delamination was observed inside the sintered body. Further, “◯” in the column of the lamination dimension indicates that the dimension after lamination was measured with a three-dimensional measuring machine, and the dimensional variation was smaller than ± 0.05%. “Δ” indicates that although there was no problem in the product dimensions, the dimensional variation was ± 0.05% or more.

  From the results of Table 11, the sample No. 5 having a hydroxyl value of the organic binder contained in the ceramic slurry to be the second ceramic green sheet layer of less than 5 KOHmg / g. In Nos. 1 and 2, delamination occurred in the sintered body, and the dimensional variation in the lamination dimension was 0.05% or more.

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

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

  Note that the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the gist of the present invention. For example, in the example of the above-described embodiment, an inorganic powder, an organic binder, and a solvent were added and mixed to produce a ceramic slurry, but a plasticizer may be added to impart flexibility to the ceramic green sheet, Further, a dispersant may be added in order to improve the dispersibility of the inorganic powder.

(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 ... 1st ceramic green sheet layer 3 ... Ceramic slurry 3 '... 2nd ceramic green sheet layer 4 ... Ceramic green sheet 5 ... Conductor layer 6 ..Ceramic green sheet laminate

Claims (13)

Forming a first ceramic green sheet layer; applying a ceramic slurry on the first ceramic green sheet layer and drying to form a second ceramic green sheet layer; forming a ceramic green sheet; A step of forming a conductor layer on the ceramic green sheet, a step of producing a ceramic green sheet laminate by laminating and heating a plurality of the ceramic green sheets on which the conductor layer is formed, and the ceramic green And a step of firing the sheet laminate, wherein the difference between the solubility parameter of the first ceramic green sheet layer and the solubility parameter of the ceramic slurry is 3 to 8, Method. 2. The method of manufacturing an electronic component according to claim 1, wherein the first ceramic green sheet layer contains a molten component that is in a molten state when heated when the ceramic green sheet laminate is manufactured. 3. The method of manufacturing an electronic component according to claim 2, wherein the melting component has a melting point of 35 to 100.degree. 3. The method of manufacturing an electronic component according to claim 2, wherein an addition amount of the organic binder contained in the first ceramic green sheet layer is 19 to 30 parts by mass with respect to 100 parts by mass of the ceramic powder. 3. The method of manufacturing an electronic component according to claim 2, wherein the organic binder contained in the first ceramic green sheet layer has a molecular weight of 80,000 to 300,000. 3. The method of manufacturing an electronic component according to claim 2, wherein an acid value of the organic binder contained in the first ceramic green sheet layer is 0.1 to 0.8 KOH mg / g. 3. The electronic component manufacturing method according to claim 2, wherein an addition amount of the organic binder contained in the ceramic slurry to be the second ceramic green sheet layer is 10 to 19 parts by mass with respect to 100 parts by mass of the ceramic powder. Method. 3. The method of manufacturing an electronic component according to claim 2, wherein the molecular weight of the organic binder contained in the ceramic slurry serving as the second ceramic green sheet layer is 100,000 to 800,000. 3. The method of manufacturing an electronic component according to claim 2, wherein the acid value of the organic binder contained in the ceramic slurry to be the second ceramic green sheet layer is 0.1 to 5 KOHmg / g. 3. The method of manufacturing an electronic component according to claim 2, wherein a glass transition point of the organic binder contained in the first ceramic green sheet layer is -20 to 0 ° C. 3. The method of manufacturing an electronic component according to claim 2, wherein the organic binder contained in the first ceramic green sheet layer has a hydroxyl value of 0.1 to 5 KOHmg / g. 3. The method of manufacturing an electronic component according to claim 2, wherein the glass transition point of the organic binder contained in the ceramic slurry to be the second ceramic green sheet layer is −20 to 20 ° C. 3. The method of manufacturing an electronic component according to claim 2, wherein the hydroxyl value of the organic binder contained in the ceramic slurry to be the second ceramic green sheet layer is 5 to 100 KOHmg / g.

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