JP2005243854A - Method of manufacturing ceramic multilayer wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent an interlayer separation and the deformation of a concave portion, to prevent a bonding defect, etc. at the mounting of an electronic component, such as an LSI, and to prevent the deformation of a conductor section of a via conductor, etc. filled in a wiring pattern and through-holes. <P>SOLUTION: The manufacture of a ceramic multilayer wiring board by stacking green sheets, each formed with the conductor section using a conductor paste, and then integrating them together and burning them, comprises the processes of forming the conductor section on the surface of each green sheet, and forming a ceramic filling layer containing the same ceramic component as the green sheet, at a portion where the conductor section is not formed; placing a resin sheet on each green sheet; stacking the green sheets; and removing the resin sheet by thermal decomposition during burning, where T<SB>a</SB>°C is the temperature at which the resin sheet reduces its weight by 80%, T<SB>b</SB>°C is the temperature at which a resin binder in the conductor paste reduces its weight by 20%, and T<SB>c</SB>°C is the temperature at which a resin binder in the ceramic filling layer reduces its weight by 20%, the relations T<SB>a</SB>≤T<SB>b</SB>and T<SB>a</SB>≤T<SB>c</SB>are satisfied. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to the manufacture of a ceramic multilayer wiring board formed by laminating a plurality of ceramic green sheets, integrating them, and firing, and more particularly, a ceramic multilayer wiring board having a recess and a wiring pattern for storing electronic components and the like. Related to the manufacture of

  Conventionally, a ceramic multilayer wiring board has a structure in which a metallized wiring layer is disposed on or inside an insulating substrate in which a plurality of insulating layers are stacked. A typical example of the ceramic multilayer wiring board having such a structure is a semiconductor element housing package for housing semiconductor elements such as IC and LSI. As such a package for housing a semiconductor element, an insulating layer made of a ceramic such as alumina ceramic is often used, and more recently, an insulating layer made of a sintered glass ceramic that can be fired simultaneously with copper metallization is laminated. Those using an insulating substrate have also been put into practical use.

  In the production of such a ceramic multilayer wiring board, a slurry is prepared by adding a suitable resin binder to a ceramic raw material powder prepared at a predetermined ratio and dispersing it in an organic solvent. A ceramic green sheet (hereinafter also referred to as a green sheet) having a predetermined thickness is formed by a casting method such as a lip coater method.

  Next, as a metallized wiring layer, a metal paste obtained by adding and mixing a resin binder, a solvent, and a plasticizer to an appropriate metal powder is printed and applied to the above green sheet in a predetermined pattern by a well-known screen printing method. At the same time, a through hole is formed by a micro drill or a laser, and a metal paste is filled in the through hole to form a through conductor (via conductor, via hole).

  Subsequent steps include (1) the case of a ceramic multilayer wiring board having recesses for storing electronic components and the like, and (2) the ceramic multilayer having conductor parts such as via conductors filled in wiring patterns or through holes other than the recesses. A description will be given separately for the wiring board.

  In the case of (1), a through hole is punched into a predetermined portion of the green sheet in order to form a recess for housing the electronic component. Thereafter, as shown in FIG. 3A in the process diagram of the conventional method, the green sheets 21a and 21b in which the through holes 20 are formed are used together with other green sheets 21c, 21d, and 21e using an appropriate adhesion liquid. A ceramic multilayer wiring board 23 as shown in FIG. 3B is obtained by firing a green sheet laminate having a plurality of layers and firing the obtained green sheet laminate under predetermined conditions.

In the case of (2), as shown in the process diagram of FIG. 4, a plurality of green sheets 25 on which conductor portions are formed are laminated together with other green sheets 26 using an appropriate adhesion liquid, and the obtained green sheet lamination The ceramic multilayer wiring board 27 is obtained by firing the body under predetermined conditions. In FIG. 4, 2 indicates a resin sheet.
JP 2003-318541 A Japanese Patent Laid-Open No. 2003-332741

  In such a ceramic multilayer wiring board (hereinafter also referred to as a board), the miniaturization of wiring patterns and via holes has been promoted in order to reduce the size of the board with the recent increase in functionality and functionality. It is essential to prevent the green sheet from being deformed. Furthermore, it is desired to cope with a form in which wiring is provided on a mounting surface of an electronic component such as an LSI chip in a concave portion of a ceramic multilayer wiring board.

  However, when a ceramic multilayer wiring board having a recess is pressed and laminated with a green sheet in which a through hole forming the recess is formed and a green sheet in which the through hole is not formed, the recess and the other part When the pressure difference is generated, the bottom of the concave portion of the green sheet laminate that is not subjected to pressure swells, which may cause a bonding failure when an electronic component is mounted on the bottom of the concave portion. In addition, if the pressure is reduced to solve this problem, the pressure necessary for the close contact of the recesses will be reduced, and peeling (delamination) will occur between the green sheets. It was difficult to obtain a high-performance substrate.

  Therefore, as a technique for solving these problems, a method of laminating a resin sheet that can be removed by thermal decomposition during firing is filled in the recesses of the green sheet laminate (FIG. 2), and conductor parts other than the recesses are protected. For this purpose, a method of arranging and laminating a resin sheet on a substrate on which a conductor portion is formed (FIG. 4) can be considered.

  In addition, as the resin binder in the green sheet in contact with the resin sheet is thermally decomposed (degreased) and the amount of the remaining resin binder in the green sheet decreases, the strength of the green sheet decreases and the brittle green sheet When the resin sheet is thermally decomposed after a delay, the melt of the high-viscosity resin sheet that has become liquefied by heating is thermally decomposed with vibration motion from top to bottom and left and right accompanying boiling on the surface of the green sheet that has become brittle after degreasing. Therefore, the surface of the green sheet in contact with the pyrolyzed portion is partially removed, and the surface is eroded and destroyed.

  In addition, with the increase in functionality and functionality, the wiring patterns and via holes formed in ceramic multilayer wiring boards, which tend to be smaller and thinner, are becoming finer. When present inside the substrate, it is difficult to completely eliminate voids caused by the difference in height due to the thickness of the conductor portion formed when the conductor portion is formed only by plastic deformation of the thin green sheet at the time of lamination. As a result, there has been a problem that an interlayer adhesion defect (delamination) and warpage deformation occur in the fired product. On the other hand, when laminating multiple ceramic multilayer wiring boards having conductor parts such as via conductors filled in wiring patterns or through holes in the surface layer part, there is a problem that the conductor part of the surface layer is crushed by the mold and deformed. This was particularly noticeable when the surface wiring was made thinner and thicker for miniaturization and resistance reduction.

  As means for solving these problems, there is a method in which a ceramic filling layer containing the same ceramic component as the ceramic layer is formed by screen printing in an area where the conductor portion is not formed, and further pressure flattening is performed (see FIG. 2). E and E in FIG.

  However, if pressure planarization is performed when the balance of viscoelasticity of the ceramic filler layer is not properly controlled, it is difficult to planarize without deforming the conductor portion adjacent to the ceramic filler layer. That is, when tan δ = (loss elastic modulus) / (storage elastic modulus) in the dry state of the ceramic packed layer is smaller than tan δ in the dry state of the conductor part, the elastic behavior is more dominant during pressurization. When stress is applied from a certain ceramic filling layer side to the conductor portion side where the viscous behavior is more dominant, the conductor portion is liable to be greatly deformed.

  The present invention has been completed in view of the above problems, and its purpose is to prevent delamination and deformation of recesses, and to prevent electrical defects such as bonding defects when mounting electronic components such as LSI chips. It is an object of the present invention to provide a method for manufacturing a ceramic multilayer wiring board, which is suitable for preventing the above. A second object is to provide a method for manufacturing a ceramic multilayer wiring board, which is suitable for preventing deformation of a conductor portion such as a via conductor filled in a wiring pattern or a through hole.

The method for producing a ceramic multilayer wiring board according to the present invention is the method for producing a ceramic multilayer wiring board obtained by laminating a plurality of ceramic green sheets each having a conductor portion formed using a conductor paste, and integrating and firing the ceramic green sheets. Forming a conductive portion on the surface of the ceramic and forming a ceramic filling layer containing the same ceramic component as the ceramic green sheet in a portion where the conductive portion is not formed, and placing a resin sheet on the ceramic green sheet a step of the steps of the ceramic green sheet laminate plurality, the resin sheet during firing and a step of removing by thermal decomposition, 80% weight loss temperature of the resin sheet T _a ° C., the conductor The 20% weight loss temperature of the resin binder contained in the paste is T _b ° C. When the 20% weight reduction temperature of the resin binder contained in the filling layer is T _c ° C, the relationship of T _a ≦ T _b and T _a ≦ T _c is satisfied.

  In the present invention, preferably, the resin sheet is thermally decomposed at 99 ° C. or more at 600 ° C.

  In the present invention, it is preferable that the resin sheet includes resin beads, a resin binder, and at least one of a plasticizer and a lubricant.

Preferably, in the present invention, the step of maintaining the 80% weight reduction temperature T _a ° C of the resin sheet during firing for a predetermined time during firing for thermal decomposition of the resin sheet, and the resin contained in the ceramic packed layer And a step of maintaining a temperature exceeding a 20% weight reduction temperature _Tc ° C of the binder for a predetermined time.

In the present invention, preferably, the method includes a step of maintaining a temperature exceeding a 20% weight reduction temperature T _b ° C of the resin binder contained in the conductor paste for a predetermined time during firing.

Further, in the present invention, preferably, the conductor paste is dried after printing, and the loss tangent tan δ represented by (loss elastic modulus) / (storage elastic modulus) is tan δ _b , and the ceramic filling layer is dried after printing. Monono the tan [delta when the tan [delta _c, characterized by satisfying the relation of tanδ _b ≦ tanδ _c.

  According to the method for producing a ceramic multilayer wiring board of the present invention, a conductor portion is formed on the surface of the green sheet, and further, a ceramic filling layer containing the same ceramic component as the green sheet is formed in a portion where the conductor portion is not formed. Since it did in this way, since the surface of a green sheet becomes substantially flat, when it pressurizes and laminates | stacks, a deformation | transformation of a green sheet can be prevented. Furthermore, since the ceramic components of the green sheet and the ceramic packed layer are made the same, the sintering temperature at the time of firing becomes the same, and there is an effect that the firing proceeds simultaneously and the adhesion is strengthened.

  In addition, since the resin sheet is arranged on the green sheet on which the conductor portion is formed, and the plurality of green sheets are pressed and stacked, the resin sheet serves as a buffer material and stacks when pressing and stacking. Sufficient pressure can be obtained almost uniformly over the entire green sheet, so that breakage of the conductor and deformation of the green sheet laminate can be prevented and the wiring pattern and via hole can be made fine. it can.

Furthermore, the 80% weight reduction temperature of the resin sheet is T _a ° C, the 20% weight reduction temperature of the resin binder contained in the conductor paste is T _b ° C, and the resin binder contained in the ceramic green sheet in contact with the resin sheet is 20% weight. Since the resin sheet satisfying the relationship of T _a ≦ T _b and T _a ≦ T _c is used when the decrease temperature is T _c ° C., most of the resin sheet is thermally decomposed when this green sheet laminate is fired. After that, the thermal decomposition of the resin binder contained in the conductor part and the green sheet that comes in contact with the resin sheet starts, so that the strength of the conductor part and the green sheet is sufficiently maintained, and the conductor part is disconnected and the green sheet is deformed in advance. It becomes possible to prevent. Further, even in the case of a substrate having a recess, a resin sheet is fitted into the through hole of the green sheet and a plurality of green sheets are pressed and laminated, so that the main surface of the green sheet becomes substantially flat and uniform on the green sheet. Pressurized pressure can be obtained, and delamination between layers and deformation of the recess can be prevented in advance. Furthermore, during firing, the strength of the conductor part and the green sheet is similarly maintained, and it is possible to prevent the conductor part from being disconnected and the green sheet from being deformed.

  Further, in the present invention, preferably, the resin sheet is thermally decomposed by 99% by weight or more at 600 ° C., so that it is more effective that the resin sheet pyrolysis residue (carbon) remains on the contact surface with the resin sheet during firing. It is possible to prevent the occurrence of electrical failure.

  Furthermore, in the present invention, preferably, since the resin sheet includes resin beads, a resin binder, and at least one of a plasticizer and a lubricant, the resin sheet containing the resin binder contains resin beads. When shearing such as punching or cutting a sheet, cracks are easily generated in the shearing direction through the resin layer existing between the resin beads, and shearing can be easily performed. Since it can be suppressed by the presence of resin beads, crack propagation to other than the shear direction can be suppressed and shear processing can be performed to a desired shape, so that it is possible to fit a resin sheet having substantially the same shape as the through hole. Deformation of the green sheet can be prevented. Furthermore, it becomes possible to further improve workability by including at least one of a plasticizer and a lubricant. By including a plasticizer, flexibility and flexibility can be imparted to the resin sheet. Moreover, since the slippage between resin or resin beads becomes good at the time of the shearing process of the resin sheet by including a lubricant, the shearing processability is improved.

Preferably, in the present invention, the step of thermally decomposing and removing the resin sheet while maintaining the 80% weight reduction temperature T _a ° C of the resin sheet for a predetermined time during firing, and 20 of the resin binder contained in the ceramic packed layer A step of maintaining a temperature exceeding the% weight reduction temperature T _c ° C for a predetermined time, so that the resin binder of the ceramic filling layer can be sufficiently thermally decomposed after the resin sheet is thermally decomposed. The disconnection due to the deformation can be prevented, and a ceramic multilayer wiring board with higher accuracy can be manufactured.

In addition, in the present invention, preferably, the method includes a step of maintaining a temperature exceeding 20% weight reduction temperature T _b ° C. of the resin binder contained in the conductor paste during firing for a predetermined time, so that after thermally decomposing the resin sheet, Since the resin binder in the conductor portion can also be sufficiently pyrolyzed, it is possible to produce a ceramic multilayer wiring board with higher accuracy by preventing disconnection due to deformation of the conductor.

Further, in the present invention, preferably, the conductor paste is dried after printing, and the loss tangent tan δ expressed by (loss elastic modulus) / (storage elastic modulus) is tan δ _b , and the ceramic filling layer is dried after printing tan δ. When tan δ _c is satisfied, the relationship of tan δ _b ≦ tan δ _c is satisfied, so that the adjacent elastic behavior is more dominant when the ceramic packed bed side where the viscous behavior is more dominant at the time of pressurization flows. It is possible to prevent deformation on the conductor part side. In addition, since unnecessary elastic stress is not applied from the ceramic filling layer side to the conductor portion side, it is possible to prevent the conductor portion from being damaged such as a crack.

  The method for producing a ceramic multilayer wiring board of the present invention will be described in detail below.

  First, a green sheet for producing a ceramic multilayer wiring board is produced as follows. Green powder powder, such as ceramic powder and glass powder, if desired, ceramic powder that serves as a sintering aid is added and mixed into the mixture, resin binder, plasticizer and other additives, organic solvent, etc. To prepare a slurry. Thereafter, a green sheet having a predetermined thickness is formed using the slurry by a forming method such as a doctor blade method, a rolling method, or a pressing method.

  Next, by punching the green sheet, a through hole serving as a via hole connecting the upper and lower wiring conductor layers is formed, and a conductor paste is filled in the through hole.

The ceramic powder includes SiO ₂ , Al ₂ O ₃ , ZrO ₂ , a composite oxide of TiO ₂ and an alkaline earth metal oxide, ZnO, MgO, MgAl ₂ O ₄ , ZnAl ₂ O ₄ , MgSiO ₃ , _{mg 2 SiO 4, Zn 2 SiO} 4, Zn 2 TiO 4, SrTiO 3, CaTiO 3, MgTiO 3, BaTiO 3, CaMgSi 2 O 6, SrAl 2 Si 2 O 8, BaAl 2 Si 2 O 8, CaAl 2 Si 2 Composite oxidation containing at least one selected from O ₈ , Mg ₂ Al ₄ Si ₅ O ₁₈ , Zn ₂ Al ₄ Si ₅ O ₁₈ , AlN, Si ₃ N ₄ , SiC, and Al ₂ O ₃ and SiO ₂ (For example, spinel, mullite, cordierite) and the like, and can be selected according to the application.

Examples of the glass powder include SiO ₂ —B ₂ O ₃ , SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ , SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ —MO (however, M Is 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 (where M ₁ and M ₂ are the same as above), SiO ₂ —B ₂ O ₃ —M ₃ O system (where M ₃ is Li, Na or K), SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ —M ₃ O system (where M ₃ is the same as above), A glass containing at least one selected from the group consisting of Pb glass, Bi glass, alkali metal oxide, alkaline earth metal oxide, and rare earth oxide is preferable. These glasses are also amorphous glass by firing, and by firing, lithium silicate, quartz, cristobalite, cordierite, mullite, anorthite, serdian, spinel, garnite, willemite, dolomite, petalite and Crystallized glass that precipitates at least one kind of crystals of the substituted derivative is used.

  The mixing ratio of the ceramic powder and the glass powder is a ratio used for a normal glass ceramic substrate material, and is preferably 60:40 to 1:99 by weight.

Examples of the auxiliary component include B ₂ O ₃ , ZnO, MnO ₂ , alkali metal oxides, alkaline earth metal oxides, rare earth metal oxides, and the like, which can be selected according to use.

  Furthermore, the resin binder of the green sheet is not particularly limited, but for example, acrylic (a homopolymer or copolymer of acrylic acid, methacrylic acid or an ester thereof, specifically an acrylic ester copolymer, methacrylic acid Ester copolymers, acrylic ester-methacrylic ester copolymers, etc.), polyvinyl acetal, cellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, polypropylene carbonate, and other homopolymers or copolymers And contains at least one selected from these.

  Specific examples of the acrylic system include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, Examples include isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isononyl acrylate, isononyl methacrylate, isodecyl acrylate, and isodecyl methacrylate. Acrylic esters and alkyl methacrylates A copolymer containing a carboxylic acid group, an alkylene oxide group, a hydroxyl group, a glycidyl group, an amino group or an amide group as a copolymerization component is preferably used as the copolymer having a steal main chain. it can.

  Examples of those having a carboxylic acid group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, and fumaric acid. Examples of those having alkylene oxide include methylene oxide, ethylene oxide, and propylene oxide. Examples of those having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerin monoacrylate, glycerin monomethacrylate, and the like. Examples of those having a glycidyl group include glycidyl acrylate and glycidyl methacrylate, and those having an amino group or an amide group. Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, N-tert-butylaminoethyl acrylate, N-tert-butylaminoethyl methacrylate, acrylamide, cyclohexylacrylamide, cyclohexylmethacrylamide, N- Examples include methylol acrylamide and diacetone acrylamide. Other copolymerizable acrylonitrile, styrene, ethylene, vinyl acetate, n-vinylpyridone and the like may be copolymerized with these copolymers having acrylic acid ester or methacrylic acid alkyl ester as the main chain.

  Specific examples of the polyvinyl acetal type include polyvinyl butyral, polyvinyl ethylal, polyvinyl propylal, polyvinyl octylal, polyvinyl phenylal, and derivatives thereof.

  Specific examples of the cellulose type include methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, nitrocellulose, and cellulose acetate.

  Next, the conductor paste for forming a conductor portion such as a metallized wiring or a via conductor is not particularly limited. For example, a metal powder such as Au, Cu, Ag, Pd, W, Mo, Ni, Al, and Pt is used. 1 type or 2 types or more are mentioned, and when it is 2 or more types, any form, such as a mixture and an alloy, may be sufficient. What mixed these resin powders with the resin binder, the solvent, the plasticizer, the dispersing agent, etc. can use it conveniently.

  It does not specifically limit as a resin binder of conductor paste, A homopolymer or copolymers, such as an acryl type, a polyvinyl acetal type, and a cellulose type, are mentioned, At least 1 sort (s) chosen from these is contained.

  Specific examples of acrylics include homopolymers or copolymers of acrylic acid, methacrylic acid or their esters, specifically acrylic ester copolymers, methacrylic ester copolymers, acrylic ester-methacrylic acid. An ester copolymer may be used, and a hydroxyl group, a carboxylic acid group, an alkylene oxide group, a glycidyl group, an amino group, an amide group, or the like may be appropriately introduced into these copolymers. By introducing these, the effect of improving the dispersibility with ceramics and the effect of improving the viscosity and thixotropy can be expected. In addition, styrene, α-methylstyrene, acrylonitrile, ethylene, vinyl acetate, polyvinyl alcohol can be copolymerized with acrylic resin as long as the performance such as thermal decomposability and solubility in various solvents is not impaired. N-vinylpyrrolidone or the like may be introduced as appropriate. Among these acrylic resins, one or two or more kinds can be appropriately selected and used as necessary.

  The solvent for the conductive paste is not particularly limited, but terpineol, dihydroterpineol, ethyl carbitol, butyl carbitol, carbitol acetate, butyl carbitol acetate, diisopropyl ketone, methyl cellosolve acetate, cellosolve acetate, butyl cellosolve, butyl Cellosolve acetate, cyclohexanone, cyclohexanol, isophorone, cypropylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butyl carbitol methyl-3-hydroxyhexanoate, trimethylpentanediol monoisobutyrate, pine oil, mineral A high boiling point solvent such as spirit can be preferably used.

  The resin binder is preferably mixed in an amount of 0.5 to 15.0 parts by weight with respect to 100 parts by weight of the metal powder, and the organic solvent is mixed in a ratio of 5 to 100 parts by weight with respect to 100 parts by weight of the solid component and the resin binder. . In addition, you may add some inorganic components, such as glass powder and oxide powder, in this conductor paste. This conductor paste is printed on the green sheet in a predetermined pattern using a known printing method such as a screen printing method or a gravure printing method.

  When manufacturing a ceramic multilayer wiring board having a plurality of ceramic layers laminated and having a conductor portion, the same ceramic component as the ceramic layer is included in a region where the conductor portion between the ceramic layers laminated with the conductor portion interposed therebetween is not formed. A ceramic packed layer (E in FIG. 2 and E in FIG. 4) is formed by a screen printing method, and then the printed surface is dried in a hot air drying furnace or a far infrared drying furnace. By performing a step of pressure flattening the obtained ceramic green sheet under heating conditions or the like, the ceramic filling layer is plastically deformed and flattened to obtain a ceramic green sheet substantially free of irregularities.

  Then, an appropriate adhesive composed of a resin binder, a solvent, and a plasticizer is applied or transferred to the green sheet, and the green sheet is pressed and laminated with another green sheet to produce a green sheet laminate. A ceramic multilayer wiring board can be obtained by firing the obtained green sheet laminate under predetermined conditions.

  Next, the ceramic filling layer used for the ceramic multilayer wiring board of the present invention will be described.

The ceramic material contained in the ceramic filling layer is basically the same ceramic as the ceramic multilayer wiring board. Accordingly, the ceramic powder includes SiO ₂ , Al ₂ O ₃ , ZrO ₂ , a composite oxide of TiO ₂ and an alkaline earth metal oxide, ZnO, MgO, MgAl ₂ O ₄ , ZnAl ₂ O ₄ , MgSiO ₃ , _{mg 2 SiO 4, Zn 2 SiO} 4, Zn 2 TiO 4, SrTiO 3, CaTiO 3, MgTiO 3, BaTiO 3, CaMgSi 2 O 6, SrAl 2 Si 2 O 8, BaAl 2 Si 2 O 8, CaAl 2 Si 2 Composite oxidation containing at least one selected from O ₈ , Mg ₂ Al ₄ Si ₅ O ₁₈ , Zn ₂ Al ₄ Si ₅ O ₁₈ , AlN, Si ₃ N ₄ , SiC, and Al ₂ O ₃ and SiO ₂ (For example, spinel, mullite, cordierite) and the like, and can be selected according to the application.

Examples of the glass powder include SiO ₂ —B ₂ O ₃ , SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ , SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ —MO (however, M Is 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 (where M ₁ and M ₂ are the same as above), SiO ₂ —B ₂ O ₃ —M ₃ O system (where M ₃ is Li, Na or K), SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ —M ₃ O system (where M ₃ is the same as above), A glass containing at least one selected from the group consisting of Pb glass, Bi glass, alkali metal oxide, alkaline earth metal oxide, and rare earth oxide is preferable. These glasses are also amorphous glass by firing, and by firing, lithium silicate, quartz, cristobalite, cordierite, mullite, anorthite, serdian, spinel, garnite, willemite, dolomite, petalite and Crystallized glass that precipitates at least one kind of crystals of the substituted derivative is used.

  The mixing ratio of the ceramic powder and the glass powder is a ratio used for a normal glass ceramic substrate material, and is preferably 60:40 to 1:99 by weight.

Examples of the auxiliary component include B ₂ O ₃ , ZnO, MnO ₂ , alkali metal oxides, alkaline earth metal oxides, rare earth metal oxides, and the like, which can be selected according to use.

  Furthermore, the resin binder of the ceramic filler layer of the present invention is not particularly limited as long as it is generally used for ceramic green sheets. For example, acrylic, polyvinyl acetal, cellulose, polyvinyl alcohol, polyvinyl acetate, A homopolymer or a copolymer such as polyvinyl chloride or polypropylene carbonate may be used, and at least one selected from these may be used, but it will be described later by using at least one acrylic. It is only necessary to adjust tan δ.

  Although it does not specifically limit as an acrylic resin, The homopolymer or copolymer of acrylic acid, methacrylic acid, or those esters, specifically, an acrylic ester copolymer, a methacrylic ester copolymer, an acrylic ester-methacrylic ester Examples include acid ester copolymers. In these copolymers, a hydroxyl group, a carboxylic acid group, an alkylene oxide group, a glycidyl group, an amino group, an amide group, or the like may be appropriately introduced. By introducing these, the effect of improving the dispersibility with ceramics and the effect of improving the viscosity and thixotropy can be expected. In addition, styrene, α-methylstyrene, acrylonitrile, ethylene, vinyl acetate, polyvinyl alcohol can be copolymerized with acrylic resin as long as the performance such as thermal decomposability and solubility in various solvents is not impaired. N-vinylpyrrolidone or the like may be introduced as appropriate. Among these acrylic resins, one or two or more kinds can be appropriately selected and used as necessary.

  Moreover, it is desirable to adjust the glass transition temperature of an acrylic resin to 20-50 degreeC, More preferably, it is good to adjust to 20-30 degreeC. Glass transition of acrylic resin containing printed matter containing acrylic resin and screen-printed ceramic packed layer with increased tan δ in dry state on conductor part, dried in hot air drying furnace or far infrared drying furnace By pressurizing under heating conditions higher than the temperature, the ceramic packed bed can be made fluid during the planarization step without increasing the amount of plasticizer and solvent, and excellent flatness can be realized.

  If the glass transition temperature of the acrylic resin is less than 20 ° C., the printed matter may remain sticky even after the drying process after screen printing, and the printed matter aggregates during the subsequent pressure flattening step under heating conditions. It tends to be transferred (attached) to the press surface by being broken or interfacial broken. On the other hand, when the glass transition temperature of the acrylic resin exceeds 50 ° C., the fluidity of the printed matter is poor when the pressure flattening step is performed at 80 ° C. or less, which is a temperature range in which the entire ceramic multilayer wiring board is not deformed. Tend to be.

  In addition, when performing the pressure flattening process under heating conditions, in order to prevent transfer (adhesion) of the printed material to the press surface, the press surface may be subjected to a peeling treatment such as fluorine treatment or silicone treatment, or the printed material and the press surface. It is desirable to provide a means for interposing a resin sheet such as PET subjected to a release treatment of silicone or wax.

  The solvent used for the ceramic packed bed of the present invention can be selected from a high boiling point solvent group generally used for screen printing. Specifically, those having a boiling point of 150 ° C. or higher are preferable, and those having a boiling point of about 200 to 250 ° C. are more preferable. When the temperature is lower than 150 ° C., the solvent volatilizes during screen printing or the like, and problems such as clogging of the screen mesh are likely to occur. On the other hand, at 250 ° C. or higher, it becomes difficult to sufficiently dry the printed matter, and the printed matter that is insufficiently dried tends to be transferred to the press surface in the pressure flattening step under heating conditions.

  The high boiling point solvent group is not particularly limited, but terpineol, dihydroterpineol, ethyl carbitol, butyl carbitol, carbitol acetate, butyl carbitol acetate, diisopropyl ketone, methyl cellosolve acetate, cellosolve acetate, butyl cellosolve, butyl Cellosolve acetate, cyclohexanone, cyclohexanol, isophorone, cypropylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butyl carbitol methyl-3-hydroxyhexanoate, trimethylpentanediol monoisobutyrate, pine oil, mineral A spirit etc. can be used conveniently.

  In general, paste for screen printing generally has a resin content of about 1 to 30 parts by weight as a resin binder with respect to 100 parts by weight of various ceramic powders, but the optimum mixing ratio varies depending on the specific gravity of the ceramic powder. Therefore, it is not limited to this range.

  The ceramic filled layer of the present invention is formed by screen printing a paste mainly composed of various ceramic powders, resin binders and a solvent. Moreover, you may add a plasticizer, a lubricant, a dispersing agent, various thixotropic agents, a thickener, etc. to the paste as needed.

  The plasticizer is not particularly limited. For example, dimethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, diheptyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, ethyl phthalyl ethyl glycol Phthalates such as butyl phthalyl butyl glycolate, aliphatic esters such as di-2-ethylhexyl adipate and dibutyl diglycol adipate, trimellitic acids such as trimellitic acid tri-2-ethylhexyl, etc. And at least one of them may be selected.

  The lubricant is not particularly limited. For example, diethylene glycol, triethylene glycol, polyethylene glycol, diethylene glycol methyl ether, triethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol-n-butyl ether, triethylene glycol-n-butyl ether, ethylene glycol phenyl Ethylene glycols such as ether, ethylene glycol-n-acetate, diethylene glycol monohexyl ether, diethylene glycol monovinyl ether, dipropylene glycol, tripropylene glycol, polypropylene glycol, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol mono D Ether, dipropylene glycol-n-butyl ether, tripropylene glycol-n-butyl ether, propylene glycol phenyl ether, ethylene glycol benzyl ether, ethylene glycol isoamyl ether and other propylene glycol systems, glycerol, diglycerol, polyglycerol and other glycerol systems, Natural waxes such as beeswax and wax, paraffin wax, microcrystalline wax, synthetic waxes such as low molecular weight polyethylene and its derivatives, fatty acids such as stearic acid and lauric acid, fatty acids such as oleic acid amide and stearic acid amide Examples include amides, fatty acid metal salts such as aluminum stearate, magnesium stearate, and calcium stearate. Both may be selected one.

  The ceramic filling layer of the present invention is formed by screen-printing the thus obtained ceramic filling layer paste on a portion where the conductor portion is not formed.

  Next, FIG. 1 is a process chart for explaining a method for producing a green sheet fitted with a resin sheet, which is a ceramic multilayer wiring board of the present invention, and each process for explaining a method for producing a ceramic multilayer wiring board of the present invention. The drawing is shown in FIG. 2, and a method for manufacturing a ceramic multilayer wiring board will be described in detail below.

  In the present invention, a resin sheet 2a that is pressurized and thermally decomposed in the firing process is fitted into the through-hole 3 before lamination. As a result, the bottom of the through hole 3 is pressurized through the resin sheet 2a in the laminating step, so that the bottom of the through hole 3 does not bulge, and high lamination pressure is applied so that delamination does not occur. It becomes possible. In addition, there is no restriction | limiting in particular about the magnitude | size of the through-hole 3 which can apply this invention, If it is a structure which can insert the resin sheet 2a, it can apply from a fine thing to a comparatively big thing.

  Next, a method for fitting the resin sheet 2a into the through hole 3 will be described. First, the through-hole 3 is formed by a punching device mainly composed of an upper mold 4 that is a driving part of the punching mold and a lower mold 6 that is a fixing part of the punching mold. As shown in FIG. 1A, the green sheet 1 is placed on the lower mold 6 provided with the opening 5, and the upper mold 4 is placed from above the green sheet 1 as shown in FIG. A punching process is performed by driving downward, and as shown in FIG.1 (c), the through-hole 3 is formed and the green sheet 1 in which the through-hole 3 was formed is obtained. The punching device may be one that can fix the upper mold and drive the lower mold.

  Next, as shown in FIG. 1 (d), using the same punching device, the resin sheet 2 is stacked on the green sheet 1 in which the through holes 3 are formed, and as shown in FIG. By driving 4, punching of the resin sheet 2 and fitting of the punched resin sheet 2 a into the through hole 3 are performed simultaneously. Subsequently, the excess resin sheet 2 is removed to obtain a green sheet A in which the resin sheet 2a is fitted in the through hole 3 as shown in FIG. 1 (f).

  Then, as shown in FIG. 2, the green sheets A1 and A2 in which the resin sheet 2a is fitted and the green sheets B1, B2 and B3 in which the wiring conductor layer 8 made of the metallized layer and the via conductor 9 are formed are laminated together. As a result, a green sheet laminate C is obtained. Next, the green sheet laminate C is fired to obtain a ceramic multilayer wiring board D.

  According to the manufacturing method of the present invention, since the bottom of the through hole 3 is not pressurized and the bottom of the through hole 3 does not bulge, it is possible to pressurize with a high lamination pressure and no delamination occurs. A ceramic multilayer wiring board D can be produced.

  On the other hand, in the case of a ceramic multilayer wiring board having a wiring pattern other than a concave portion or a conductor portion such as a via conductor filled in a through hole, as shown in the process diagram of FIG. The resin sheet 2 serves as a cushion by placing the resin sheet 2 on the green sheet 25 on which the conductor portion is formed and laminating by pressing the green sheet 26 before laminating a plurality of layers together with the green sheet 26 using an appropriate adhesion liquid. By satisfying the above, it is possible to prevent a problem that the surface conductor part is crushed and deformed by the mold and a problem that a defect such as disconnection occurs in the conductor part of the surface layer. A ceramic multilayer wiring board 27 is obtained by firing the obtained green sheet laminate under predetermined conditions.

  Next, a method for producing the resin sheet 2 (2a) will be described. The resin sheet 2 in the present invention preferably includes resin beads, a resin binder, and at least one of a plasticizer and a lubricant. For the performance required for resin sheets, punching processability (shearing processability) and thermal decomposability in the firing process are important. In order to obtain good punching processability, the addition of powdered resin beads is effective. is there. The resin beads are not particularly limited as long as they exhibit good thermal decomposition behavior upon firing, but acrylic and α-methylstyrene are preferred. The average particle size of the resin beads is preferably 1 to 20 μm. When the average particle diameter is 1 μm or less, aggregation of resin beads becomes a problem, and when the average particle diameter is 20 μm or more, protrusions are likely to occur on the surface of the resin sheet 2 (2a). In addition, you may use the thing of a hollow structure as a form of the resin bead.

  Further, the resin beads preferably have a crosslinking reaction from the viewpoint of solvent resistance. However, when the crosslinking reaction proceeds excessively, the thermal decomposability tends to deteriorate.

  Resin beads and resin binders such as aromatic hydrocarbons such as toluene, benzene and xylene, esters such as ethyl acetate, butyl acetate and isobutyl acetate, ketones such as methyl isobutyl ketone, methyl ethyl ketone and acetone, hexane and heptane, etc. One or more selected from aliphatic hydrocarbons, ethers such as diethyl ether, dipropyl ether, and tetrahydrofuran, alcohols such as methanol, ethanol, isopropyl alcohol, and butanol, cell solves such as ethyl cellosolve, etc. Disperse in organic solvent.

  The resin binder used for the resin sheet 2 (2a) is not particularly limited as long as it has excellent thermal decomposability, but acrylic, α-methylstyrene, and the like are preferable. As acrylic resins, homopolymers or copolymers of acrylic acid, methacrylic acid or their esters, specifically acrylic ester copolymers, methacrylic ester copolymers, acrylic ester-methacrylic ester copolymers Examples include coalescence. As such, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate , T-butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and the like. Among these acrylic resins, one or two or more kinds can be appropriately selected and used as necessary. Among these, an isobutyl methacrylate-based (IBMA) or methyl methacrylate-based (MMA) resin binder alone or a copolymer is particularly preferable. In addition, styrene, α-methylstyrene, acrylonitrile, ethylene, or the like, which can be copolymerized with an acrylic resin, may be appropriately introduced as long as the thermal decomposability is not impaired. It contains at least one selected from these.

  Furthermore, the plasticizer added to give flexibility and flexibility to the resin sheet 2 (2a) is not particularly limited as long as it does not impair the thermal decomposability of the resin sheet 2 (2a). Phthal such as dimethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, diheptyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate There are acid ester type and aliphatic ester type such as di-2-ethylhexyl adipate and dibutyl diglycol adipate, and contains at least one selected from these. Among them, plasticizers such as phthalic acid esters such as dibutyl phthalate (DBP) and di-2-ethylhexyl phthalate (DOP) are preferable.

  Furthermore, the lubricant added to improve the shear processability of the resin sheet 2 (2a) is not particularly limited as long as it does not impair the thermal decomposability of the resin sheet 2 (2a). Ethylene glycol, polyethylene glycol, diethylene glycol methyl ether, triethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol-n-butyl ether, triethylene glycol-n-butyl ether, ethylene glycol phenyl ether, ethylene glycol-n-acetate, diethylene glycol monohexyl ether , Ethylene glycols such as diethylene glycol monovinyl ether, dipropylene glycol, tripropylene glycol, polypropylene Ren glycol, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol monoethyl ether, dipropylene glycol-n-butyl ether, tripropylene glycol-n-butyl ether, propylene glycol phenyl ether, ethylene glycol benzyl ether, ethylene glycol Examples include propylene glycols such as isoamyl ether, and glycerols such as glycerin, diglycerin, and polyglycerin, and at least one selected from these. Of these, polyethylene glycol (PEG) and glycerin are preferable.

  These plasticizers and lubricants are preferably limited to the minimum necessary amount. When many of these remain in the composition of the melted resin sheet 2 (2a) at the time of firing, the resin binder in the conductor part in contact with it tends to dissolve and the strength of the conductor part decreases. There is a possibility that defects such as deformation or disconnection of the conductor portion may occur.

  A slurry prepared by adding 40 to 80 parts by weight of a resin binder to 100 parts by weight of the resin beads in the organic solvent and dispersing it, and then adding 5 to 40 parts by weight of a plasticizer and a lubricant in a total amount. The resin sheet 2 (2a) is obtained by applying onto a carrier sheet that has been treated with a release agent by a coating method such as a conventionally known roll coater, gravure coater, blade coater, and drying.

  It is preferable that the thermal decomposability of the resin sheet 2 (2a) is superior to the resin binder contained in the conductor paste for forming the conductor portion adjacent to the resin sheet 2 (2a). Thereby, after most of the resin sheet 2 (2a) is thermally decomposed at the time of firing, the thermal decomposition of the resin binder of the conductor paste contained in the conductor portion is started, so that a large amount of the molten resin sheet 2 (2a) In the stage where the composition remains, the resin binder in the conductor part in contact with the composition has not started thermal decomposition, so that the strength of the conductor part is sufficiently maintained. Therefore, a highly reliable ceramic multilayer wiring board free from defects such as the composition of the melted resin sheet 2 (2a) dissolving the resin binder in the conductor and deforming or breaking the conductor. It can be produced.

  On the other hand, it is preferable that the thermal decomposability of the resin sheet 2 (2a) is superior to the resin binder contained in the ceramic filler layer that comes into contact with the resin sheet 2 (2a) except for the conductor portion. That is, as the resin binder in the ceramic packing layer is thermally decomposed (degreasing) and the amount of the residual resin binder in the ceramic packing layer decreases, the strength of the green sheet decreases and delays on the brittle ceramic packing layer. When the resin sheet 2 (2a) is thermally decomposed, the melt of the high-viscosity resin sheet 2 (2a), which has become liquid by heating, moves up, down, left and right accompanying boiling on the surface of the ceramic packed layer that has become brittle after degreasing. Therefore, the surface of the ceramic packed layer in contact with the thermally decomposed portion is partially removed, so that the phenomenon that the surface is eroded and destroyed can be eliminated.

Therefore, the resin sheet 2 (2a) is subjected to differential thermogravimetric differential thermal analysis (TG / DTA) up to 600 ° C. in a N ₂ atmosphere at a temperature rising rate of 10 ° C./min (manufactured by Rigaku Corporation). In the case of “TG8120”), the 80% weight reduction temperature of the resin sheet 2 (2a) is T _a ° C, the 20% weight reduction temperature of the resin binder contained in the conductor paste is T _b ° C, and the ceramic filling layer contains When the 20% weight loss temperature of the resin binder is T _c ° C, the relationship of T _a ≦ T _b and T _a ≦ T _c is satisfied. Furthermore, it is preferable that the resin sheet 2 (2a) thermally decomposes 99% by weight or more at 600 ° C. or lower.

It should be noted that the temperature profile of the debinding step during firing of the ceramic multilayer wiring board of the present invention is sufficiently high by maintaining the temperature for a predetermined time in the vicinity of T _a ° C, which is the temperature at which most resin sheets 2 (2a) are thermally decomposed. After the thermal decomposition and removal of the resin sheet 2 (2a), a temperature region exceeding T _b ° C where the resin binder in the conductor portion starts thermal decomposition and a temperature exceeding T _c ° C where the resin binder in the ceramic packed layer starts thermal decomposition. The temperature is preferably maintained in the region for a predetermined time, for example, 1 to 6 hours. As a result, after most of the resin sheet 2 (2a) is sufficiently thermally decomposed, the resin binder of the conductor portion and the ceramic filling layer can start to decompose, and the molten resin sheet 2 (2a) At the stage where the composition remains, since the resin binder in the conductor part and the ceramic filler layer has not started thermal decomposition, sufficient strength can be maintained. Therefore, the composition of the melted resin sheet 2 (2a) can be prevented from eroding and destroying the conductor portion and the ceramic filling layer that are in contact therewith. Moreover, the resin binder of a ceramic filling layer can also be fully thermally decomposed by maintaining for a predetermined time, for example, 1 hour to 6 hours, in a temperature region exceeding T _c ° C.

Furthermore, the resin binder of the conductor portion can be sufficiently thermally decomposed by maintaining it in a temperature range exceeding T _b ° C for a predetermined time, for example, 1 to 6 hours.

  The time for thermally decomposing such a resin component is determined conveniently depending on the amount and material of the resin, and is not particularly limited.

  Examples of the method for producing a ceramic multilayer wiring board according to the present invention will be described below.

(Examples 1 to 9) Ceramic multilayer wiring board having recesses for storing electronic components and the like [1. Preparation of green sheet]
11 parts by mass of the resin binder shown in Table 1 and 5 parts by mass of dibutyl phthalate as a plasticizer with respect to 100 parts by mass of the glass ceramic raw material powder composed of SiO ₂ , Al ₂ O ₃ , CaO, ZnO, B ₂ O ₃ Then, toluene was mixed as an organic solvent by a ball mill for 36 hours to prepare a slurry. The obtained slurry was molded by the doctor blade method and dried to produce a green sheet having a thickness of 0.3 mm. Next, a through hole having a diameter of 200 μm was formed in the green sheet by punching.

  Subsequently, the through-hole filling conductor paste described below was filled into the through-hole formed in the green sheet by a screen printing method. Next, a wiring pattern having a film thickness of 25 μm was printed and applied by screen printing using the following conductive paste for wiring, followed by drying at 80 ° C. for 1 hour using a hot air drying furnace to form a metallized wiring. .

Next, 100 parts by weight of glass ceramic raw material powder composed of SiO ₂ , Al ₂ O ₃ , CaO, ZnO, and B ₂ O ₃ is mixed with 5 parts by weight of a resin binder shown in Table 1, terpineol and butyl carbitol acetate. 20 parts by weight of a solvent and 20 parts by weight of a phthalate ester plasticizer (mixture of DOP and DBP) were added, and these were stirred and mixed. Then, a ceramic filler layer paste is prepared by mixing with a three-roll mill until there is no aggregate of ceramic powder and resin binders, and a ceramic filler layer E is formed by screen printing in an area where no conductor part is formed. Then, it was dried at 80 ° C. for 1 hour using a warm air drying furnace to produce a green sheet.

[2. Preparation of conductor paste]
2-1) Through-hole filling conductor paste (for via conductor formation)
100 parts by mass of Cu powder 2 parts by weight of resin binder shown in Table 1, 4 parts by weight of mixed solvent of terpineol and butyl carbitol acetate, 2 parts by weight of phthalate ester plasticizer (mixture of DOP and DBP) A portion was added, and these were stirred and mixed. Thereafter, a conductor paste was prepared by mixing with a three-roll mill until there was no aggregate of Cu powder and resin binders.

2-2) Conductor paste for wiring 100 parts by weight of Cu powder 3 parts by weight of resin binder (used in common with via conductor part) shown in Table 1, 10 parts by weight of mixed solvent of terpineol and butyl carbitol acetate 10 parts by weight of a phthalate ester plasticizer (mixture of DOP and DBP) was added, and these were stirred and mixed. Thereafter, a conductor paste was prepared by mixing with a three-roll mill until there was no aggregate of Cu powder and resin binders.

[3. Preparation of resin sheet]
A composition obtained by adding 55 parts by weight of isobutyl methacrylate, 5 parts by weight of DOP, 5 parts by weight of polyethylene glycol, and 150 parts by weight of methyl isobutyl ketone as a resin binder to 100 parts by weight of resin beads of crosslinked isobutyl methacrylate was mixed to form a slurry. . The slurry was molded by the doctor blade method and dried to prepare a resin sheet 2 having a thickness of 300 μm.

[4. Fabrication of ceramic multilayer wiring board with recesses]
The green sheet laminate of FIG. 2 was formed using the resin sheet 2. That is, the resin sheets 2a are respectively fitted to the green sheets A1 and A2 (length 50 mm × width 50 mm × thickness 0.3 mm, through hole portion: length 2 mm × width 2 mm × depth 0.3 mm) by the punching method of FIG. It was crowded.

Subsequently, green sheets A1, A2, B1, B2, and B3 coated with an adhesive made of an acrylic resin, a solvent, and a phthalate ester plasticizer are pressed and laminated at a pressure of 4.9 × 10 ⁶ Pa. Five green sheets were integrated to produce a green sheet laminate having internal wiring. Then, the laminated body was placed on the Al ₂ O ₃ based setter nitrogen - hydrogen - a mixed atmosphere firing furnace of steam, at 310 ° C. is about 80% weight loss temperature T _a ° C. of the resin sheet 2 After sufficiently removing the resin sheet by holding for 3 hours, the resin binder contained in the ceramic filler layer has a 20% weight reduction temperature T _c ° C and the resin binder contained in the conductor paste has a 20% weight reduction temperature T _b ° C. The binder was further removed by holding at 850 ° C., which is a temperature region exceeding 3 hours, and then baked at 950 to 1000 ° C.

(Comparative Examples 1-8)
The resin binder of the ceramic filling layer in Examples 1 to 9 and the resin binder of the conductive paste are those shown in Table 1, and the same procedure as in Examples 1 to 9 except that ethyl cellulose is used as the resin binder of the resin sheet. A ceramic multilayer wiring board was produced. The firing was carried out at 350 ° C. for 3 hours to sufficiently remove the resin sheet, and then held at 850 ° C. for 3 hours to further remove the binder, followed by 950 to 1000 ° C.

(Comparative Example 9)
A ceramic multilayer wiring board was produced in the same manner as in Examples 1 to 9 except that the resin sheet 2 was not fitted.

(Comparative Example 10)
A ceramic multilayer wiring board was produced in the same manner as in Examples 1 to 9 except that the ceramic filling layer was not formed.

Table 1 shows the resin binder components of the ceramic filler layer, conductor paste, and resin sheet used in Examples 1 to 9 and Comparative Examples 1 to 10, and their thermogravimetric differential thermal analysis results. The thermogravimetric differential thermal analysis is performed by performing differential thermogravimetric differential thermal analysis (TG / DTA) up to 600 ° C. at a heating rate of 10 ° C./min in a N ₂ atmosphere (manufactured by Rigaku Denki Co., Ltd.). TG8120 "). A rheology measuring device (model: MCR300, manufactured by PHYSICA) was used for measuring tan δ represented by (loss elastic modulus) / (storage elastic modulus) of the ceramic filler layer and the conductor portion.

The ceramic filling layer and the conductor paste to be the conductor part were each printed with a screen printer so as to form a sheet having a thickness of 100 μm, and then dried at 80 ° C. for 1 hour using a warm air drying furnace. A plate-shaped sample having a thickness of 0.5 mm and a diameter of 20 mm is obtained by setting the sheet from which the dried sheet-like material has been peeled off to a die of a press molding machine and pressurizing with a pressure of 4.9 × 10 ⁶ Pa. Was prepared as a measurement sample.

Then, the strain changed by sweeping from 0 to 100% at a frequency of 100 Hz was given to the measurement sample under a constant temperature condition of 60 ° C., and the storage elastic modulus and the loss elastic modulus were measured. When such a sinusoidal distortion is applied to the elastic body, the viscous body is 90 degrees out of phase, while the viscous body is 90 degrees out of phase. The phase shifts from 0 to 90 degrees with respect to the applied distortion. Using this fact, tan δ = (loss elastic modulus) / (storage elastic modulus) was obtained.

Table 2 shows the evaluation results of the ceramic multilayer wiring board obtained. First, the state of the conductor part at the bottom of the recess was observed with a scanning electron microscope to confirm the presence or absence of an abnormality. Furthermore, the continuity test of the conductor part was performed, the presence or absence of a disconnection was confirmed, and the defect rate was calculated | required. Moreover, the surface state of the ceramic filling layer which contacts a resin sheet was observed with the scanning electron microscope, and the presence or absence of abnormality was confirmed. On the other hand, the bottom shape of the recess was measured with a high-speed three-dimensional shape measurement system (model: EMS98AD-3D100XY, manufactured by Combs), and the maximum height difference was defined as the bottom maximum warp value. Moreover, it was observed with a scanning electron microscope whether the wall portion surrounding the concave portion was deformed. Finally, the ceramic multilayer wiring board was cut, and the presence or absence of interlayer adhesion failure was observed with a scanning electron microscope.

From Table 2, in Examples 1 to 9, the 80% weight reduction temperature of the resin sheet is T _a ° C., the 20% weight reduction temperature of the resin binder contained in the conductor paste is T _b ° C., and the ceramic filling layer in contact with the resin sheet. _Satisfying the relationship of T _a ≦ T _b and T _a ≦ T _c when the 20% weight reduction temperature of the resin binder contained in the resin binder is T _c ° C., and the resin sheet has a heat of 99 wt% or higher at 600 ° C. or lower. As a result of decomposition, no abnormalities were found in the conductor portion and the portion other than the conductor portion arranged at the bottom of the concave portion, and a good fired body without residue (carbon) after decomposition could be obtained.

On the other hand, in Comparative Examples 1, 3, 4, 5, 7, and 8, since T _a > T _b and T _a > T _c , the resin binder in the conductor portion and the ceramic packed layer is accompanied by thermal decomposition. After the strength decreases due to the decrease, the resin sheet begins to thermally decompose with a delay, and the ceramic filling layer that contacts the conductor part and the resin sheet is eroded and destroyed, the surface condition is roughened, and the bottom warp of the recess is slightly increased. It became. Moreover, since a part of conductor part melt | dissolved, the disconnection rate rose. Moreover, the carbide | carbonized_material by the thermal decomposition residue of the resin sheet remained in the bottom part of the through-hole.

In Comparative Examples 2 and 6, while satisfying the relationship of T _a ≦ T _b , since T _a > T _c , no abnormality was observed in the conductor portion, but the resin binder in the ceramic packed layer was thermally decomposed. After the strength decreased due to the decrease, the resin sheet started to thermally decompose with a delay, and the ceramic filling layer in contact with the resin sheet was eroded and destroyed, and the surface state was roughened. became. Moreover, the carbide | carbonized_material by the thermal decomposition residue of the resin sheet remained in the bottom part of the through-hole.

  In Examples 1 to 9 and Comparative Examples 1 to 8 and 10, since the green sheet was pressed and laminated in a state where the resin sheet was fitted, the maximum bulge warp at the bottom of the recess was kept low. Although no adhesion failure was observed between the ceramic layers, in Comparative Example 9, since the resin sheet was not used, the maximum value of the warpage of the recesses was high. Also, poor adhesion between the ceramic layers was observed.

In Comparative Example 5, since tan δ _b > tan δ _c , stress acts from the ceramic packed layer side where the elastic behavior is more dominant at the time of pressurization to the conductor portion side where the adjacent viscous behavior is more dominant, As a result, deformation was observed in the conductor portion. In addition, since the conductor part was eroded and destroyed due to the thermal decomposition of the resin sheet, the disconnection rate increased significantly.

  In Comparative Example 10, since the ceramic filling layer was not formed, the level difference caused by the height of the internal wiring of about 25 μm could not be canceled by the plastic deformation of the green sheet at the time of lamination. Inadequate adhesion was observed.

(Examples 10 to 18) Ceramic multilayer wiring board having no recess [1. Preparation of green sheet]
11 parts by mass of the resin binder shown in Table 3 and 5 parts by mass of dibutyl phthalate as a plasticizer with respect to 100 parts by mass of the glass ceramic raw material powder composed of SiO ₂ , Al ₂ O ₃ , CaO, ZnO, B ₂ O ₃ Then, toluene was mixed as an organic solvent by a ball mill for 36 hours to prepare a slurry. The obtained slurry was molded by a doctor blade method and dried to produce a green sheet having a thickness of 0.3 mm. Next, a through hole having a diameter of 200 μm was formed in the green sheet by punching.

  Subsequently, the through-hole filling conductor paste described below was filled into the through-hole formed in the green sheet by a screen printing method. Next, a wiring pattern having a film thickness of 25 μm was printed and applied by screen printing using the following conductive paste for wiring, followed by drying at 80 ° C. for 1 hour using a hot air drying furnace to form a metallized wiring. .

Next, 100 parts by weight of glass ceramic raw material powder composed of SiO ₂ , Al ₂ O ₃ , CaO, ZnO, and B ₂ O ₃ is mixed with 5 parts by weight of a resin binder shown in Table 1, terpineol and butyl carbitol acetate. 20 parts by weight of a solvent and 20 parts by weight of a phthalate ester plasticizer (mixture of DOP and DBP) were added, and these were stirred and mixed. Then, a ceramic filler layer paste is prepared by mixing with a three-roll mill until there is no aggregate of ceramic powder and resin binders, and a ceramic filler layer E is formed by screen printing in an area where no conductor part is formed. Then, it was dried at 80 ° C. for 1 hour using a warm air drying furnace to produce a green sheet.

[2. Preparation of conductor paste]
2-1) Through-hole filling conductor paste (for via conductor formation)
100 parts by mass of Cu powder 2 parts by weight of resin binder shown in Table 3, 4 parts by weight of mixed solvent of terpineol and butyl carbitol acetate, 2 parts by weight of phthalate ester plasticizer (mixture of DOP and DBP) A portion was added, and these were stirred and mixed. Thereafter, a conductor paste was prepared by mixing with a three-roll mill until there was no aggregate of Cu powder and resin binders.

2-2) Conductor paste for wiring 100 parts by weight of Cu powder 3 parts by weight of resin binder (used in common with via conductor part) shown in Table 3 and 10 parts by weight of mixed solvent of terpineol and butyl carbitol acetate 10 parts by weight of a phthalate ester plasticizer (mixture of DOP and DBP) was added, and these were stirred and mixed. Thereafter, a conductor paste was prepared by mixing with a three-roll mill until there was no aggregate of Cu powder and resin binders.

[3. Preparation of resin sheet]
A composition obtained by adding 55 parts by weight of isobutyl methacrylate, 5 parts by weight of DOP, 5 parts by weight of polyethylene glycol, and 150 parts by weight of methyl isobutyl ketone as a resin binder to 100 parts by weight of resin beads of crosslinked isobutyl methacrylate was mixed to form a slurry. .

  The slurry was molded by the doctor blade method and dried to prepare a resin sheet 2 having a thickness of 300 μm.

[4. Fabrication of ceramic multilayer wiring board having no recesses]
An adhesive made of an acrylic resin, a solvent, and a phthalate ester plasticizer is applied to the green sheets 25 and 26 in which the wiring patterns and through holes are formed with the above-mentioned conductor paste, and is applied at a pressure of 4.9 × 10 ⁶ Pa. When the two green sheets were integrated by pressing and laminating, the resin sheet 2 was placed on the green sheet 25 of the outermost layer portion to produce a green sheet laminate having a conductor portion. Then, the laminated body was placed on the Al ₂ O ₃ based setter nitrogen - hydrogen - a mixed atmosphere firing furnace of steam, at 310 ° C. is about 80% weight loss temperature T _a ° C. of the resin sheet 2 After sufficiently removing the resin sheet by holding for 3 hours, the resin binder contained in the ceramic filler layer has a 20% weight reduction temperature T _c ° C and the resin binder contained in the conductor paste has a 20% weight reduction temperature T _b ° C. The binder was further removed by holding at 850 ° C., which is a temperature region exceeding 3 hours, and then baked at 950 to 1000 ° C.

(Comparative Examples 11-18)
In the same manner as in Examples 10 to 18 except that the green sheet resin binder and conductor paste resin binder shown in Table 1 were used in Examples 10 to 18 and ethyl cellulose was used as the resin binder of the resin sheet. A multilayer wiring board was produced. In addition, baking was hold | maintained at 350 degreeC for 3 hours, and after performing the binder removal process of a resin sheet fully, it hold | maintained at 850 degreeC for 3 hours, and further debindered, and was continuously performed at 950-1000 degreeC.

(Comparative Example 19)
A ceramic multilayer wiring board was produced in the same manner as in Examples 10 to 18 except that the resin sheet 2 was not placed.

(Comparative Example 20)
A ceramic multilayer wiring board was produced in the same manner as in Examples 10 to 18 except that the ceramic filling layer was not formed.

Table 3 shows the resin binder components of the green sheets, conductor pastes, and resin sheets used in Examples 10 to 18 and Comparative Examples 11 to 20, and their thermogravimetric differential thermal analysis results. The thermogravimetric differential thermal analysis is performed by performing differential thermogravimetric differential thermal analysis (TG / DTA) up to 600 ° C. at a heating rate of 10 ° C./min in a N ₂ atmosphere (manufactured by Rigaku Denki Co., Ltd.). TG8120 "). In addition, for the measurement of tan δ represented by (loss elastic modulus) / (storage elastic modulus) of the ceramic filler layer and the conductor part, a rheology measuring device (model: MCR300, manufactured by PHYSICA) was used. The same measurement as in No. 9 was performed.

Table 4 shows the evaluation results of the ceramic multilayer wiring board obtained. First, the state of the conductor portion on the outermost layer was observed with a scanning electron microscope to confirm the presence or absence of abnormality. Furthermore, the height of the outermost layer wiring was measured with a high-speed three-dimensional shape measurement system. Moreover, the continuity test of the conductor part was performed, the presence or absence of a disconnection was confirmed, and the defect rate was calculated | required. On the other hand, the surface state of the ceramic packed layer in contact with the resin sheet was observed with a scanning electron microscope to confirm the presence or absence of abnormality. Finally, the ceramic multilayer wiring board was cut, and the presence or absence of interlayer adhesion failure was observed with a scanning electron microscope.

From Table 4, in Examples 10 to 18, satisfies the relationship _{T a} ≦ _{T b} and _{T a} ≦ _{T c,} further, the resin sheet is thermally decomposed above 99 wt% at 600 ° C. or less, are arranged as the outermost layer No abnormalities were found in the ceramic filler layer in contact with the conductor part and the resin sheet, and a good fired body without residue (carbon) after decomposition could be obtained.

On the other hand, in Comparative Examples 11, 13, 14, 15, 17, and 18, since T _a > T _b and T _a > T _c , the resin binder in the conductor portion and the ceramic packed layer is accompanied by thermal decomposition. After the strength decreased due to the decrease, the resin sheet started to thermally decompose with a delay, and the ceramic filler layer in contact with the conductor portion and the resin sheet was eroded and destroyed. Moreover, since a part of conductor part melt | dissolved, the disconnection rate rose. In the outermost layer portion, carbides due to the thermal decomposition residue of the resin sheet remained.

In Comparative Examples 12 and 16, while satisfying the relationship of T _a ≦ T _b , since T _a > T _c , no abnormality was observed in the conductor portion, but the resin binder in the ceramic packed layer was thermally decomposed. After the strength decreased due to the decrease, the resin sheet started to thermally decompose with a delay, and the ceramic packed layer in contact with the resin sheet was eroded and destroyed. Moreover, the carbide | carbonized_material by the thermal decomposition residue of a resin sheet remained in the outermost layer part.

  In Examples 10 to 18 and Comparative Examples 11 to 18 and 20, since the green sheet was pressed and laminated in a state where the resin sheet was placed on the outermost layer part, the conductor part of the outermost layer part was protected. However, in Comparative Example 19, since the resin sheet was not used, the wiring of the outermost layer part was subjected to compression deformation at the time of pressurization, and thus the wiring height was slightly lowered.

In Comparative Example 15, since tan δ _b > tan δ _c , the stress acts from the ceramic packed layer side where the elastic behavior is more dominant at the time of pressurization to the conductor portion side where the adjacent viscous behavior is more dominant, As a result, deformation was observed in the conductor portion. In addition, since the conductor part was eroded and destroyed due to the thermal decomposition of the resin sheet, the disconnection rate increased significantly.

  In Comparative Example 20, since the ceramic filling layer was not formed, the step caused by the height of the internal wiring of about 25 μm could not be canceled by the plastic deformation of the green sheet at the time of lamination. Inadequate adhesion was observed.

(A)-(f) is each process drawing explaining the preparation methods of the green sheet in which the resin sheet used as the ceramic multilayer wiring board of this invention was engage | inserted. (A)-(c) is each process drawing explaining the manufacturing method of the ceramic multilayer wiring board which has a recessed part of this invention. (A), (b) is each process drawing explaining the manufacturing method of the ceramic multilayer wiring board which has the conventional recessed part. (A)-(d) is each process drawing explaining the manufacturing method of the ceramic multilayer wiring board which does not have a recessed part of this invention.

Explanation of symbols

1: Ceramic green sheet 2: Resin sheet 2a: Resin sheet 3: Through hole 4: Upper mold 5: Opening 6: Lower mold 7: Recess 8: Wiring conductor layer 9: Via conductors A, A1, A2: Ceramic green Sheet B1, B2, B3: Ceramic green sheet C: Ceramic green sheet laminate D: Ceramic multilayer wiring board E: Ceramic filling layer 20: Through holes 21a, 21b: Ceramic green sheets 21c, 21d, 21e: Ceramic green sheet 22: Recess 23: Ceramic multilayer wiring board 24: Delamination (delamination)
25, 26: Ceramic green sheet 27: Ceramic multilayer wiring board

Claims (6)

When manufacturing a ceramic multilayer wiring board formed by laminating a plurality of ceramic green sheets each having a conductor portion formed using a conductor paste, and firing them, the conductor portion is formed on the surface of the ceramic green sheet and the conductor portion Forming a ceramic filling layer containing the same ceramic component as the ceramic green sheet, a step of placing a resin sheet on the ceramic green sheet, and laminating a plurality of the ceramic green sheets And a step of thermally decomposing and removing the resin sheet during firing, the 80% weight reduction temperature of the resin sheet is T _a ° C, and the resin binder contained in the conductor paste is 20% weight reduction temperature _Tb C, 20% weight reduction of resin binder contained in the ceramic packed layer A method for producing a ceramic multilayer wiring board, wherein the relationship of T _a ≦ T _b and T _a ≦ T _c is satisfied when the temperature is T _c ° C. The method for producing a ceramic multilayer wiring board according to claim 1, wherein the resin sheet is thermally decomposed at 99% by weight or more at 600 ° C. 3. The method for manufacturing a ceramic multilayer wiring board according to claim 1, wherein the resin sheet includes resin beads, a resin binder, and at least one of a plasticizer and a lubricant. A step of thermally decomposing and removing the resin sheet while maintaining an 80% weight reduction temperature T _a ° C of the resin sheet for a predetermined time during firing, and a 20% weight reduction temperature T of the resin binder contained in the ceramic packed layer _The method for manufacturing a ceramic multilayer wiring board according to claim 1, further comprising a step of maintaining a temperature exceeding _c ° C. for a predetermined time. The ceramic according to any one of claims 1 to 4, further comprising a step of maintaining a temperature exceeding a 20% weight reduction temperature T _b ° C of the resin binder included in the conductor paste for a predetermined time during firing. A method for manufacturing a multilayer wiring board. When the although the conductive paste was dried after printing (loss modulus) / loss tangent tan [delta represented by (storage modulus) tan [delta _b, the tan [delta but dried after printing the ceramic filling layer was tan [delta _c The method for producing a ceramic multilayer wiring board according to claim 1, wherein the relationship of tan δ _b ≦ tan δ _c is satisfied.

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