JP2005072500A - Composite sheet, laminate, method for manufacturing them, and laminated part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To simultaneously satisfy the reduction of the thickness of an insulating layer and the increase of the thickness of a wiring conductor layer, and also to enable the accurate formation of functional ceramic parts such as a chip capacitor in a substrate. <P>SOLUTION: An unbaked functional ceramic 12 is mounted on a light transmitting carrier film 10; a photosetting slurry at least containing a photosetting monomer, a photopolymerization initiator, and a ceramic material is coated on the carrier film 10 having the functional ceramic parts 12 formed thereon to have a thickness not smaller than the thickness of the functional ceramic 12, and to form a photosetting ceramic layer 13; and the carrier film 10 is irradiated with light from its back side to photoset a region of the film other than the formation of the functional ceramic parts 12. Thereafter, a non-photoset is melted and removed to prepare a composite sheet 'a' having the photosetting ceramic layer 13 and the functional ceramic 12. The sheet is stacked on another composite sheet similarly manufactured. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a composite sheet or laminate suitable for ceramic laminated parts and laminated substrates used in mobile communication devices and the like, and a method for producing them.

  In recent years, electronic devices are becoming smaller and lighter and more portable, and circuit blocks used for such electronic devices are also becoming smaller and more complex, and the density and size of laminated parts such as ceramic multilayer substrates are increasing. It is being advanced. In this trend, ceramic multilayer substrates suitable for high-frequency modules are widely used because of their low dielectric loss and built-in passive elements such as capacitors, and in order to promote further miniaturization, A ceramic substrate having a high dielectric constant layer and a magnetic layer built into a specific part of the substrate is being studied.

  Conventional ceramic multilayer substrates are usually manufactured by a manufacturing method called a green sheet method. In this green sheet method, a green sheet is prepared by a doctor blade method or the like using a slurry containing ceramic powder as an insulating layer, and then the NC sheet or NC die is placed on the green sheet at a position to be a via hole conductor. A plurality of green sheets formed in the same manner after forming a through hole, printing a wiring pattern on the inside and surface using a conductor paste, filling the through hole with a conductor paste to form a via-hole conductor Is a manufacturing method in which the laminate is simultaneously fired.

  In order to incorporate functional ceramic parts such as high dielectric constant layers and magnetic layers in this green sheet method, in addition to insulating green sheets, high dielectric ceramic materials, magnetic ceramic materials, etc. are used to separate green sheets. It is manufactured and laminated with an insulating green sheet (in particular, refer to Patent Documents 1 and 2), or a concave portion is formed at a predetermined position of the insulating green sheet with an NC punch or a die, and a high dielectric constant. It has also been studied to fill and form a ceramic paste or magnetic ceramic paste (see Patent Document 3 in particular).

  Also, in the green sheet method, in response to the demand for higher precision and higher density, the insulation layer thickness between the insulation layers of the insulation layer is reduced, and the loss and reduction of the interconnection conductor layer are reduced. In order to realize the resistance value, it is required to increase the thickness of the wiring conductor layer.

  However, in a conventional manufacturing method such as the green sheet method, a wiring conductor layer is formed when it is attempted to satisfy the two requirements of reducing the thickness of the insulating layer and increasing the thickness of the wiring conductor layer at the same time. A step corresponding to the thickness of the wiring conductor layer inevitably occurs between the portion and the portion not formed.

  Due to this step, stacking faults (delamination) may occur, or even if the step is filled by forcibly pressing, there is a problem that a partial density difference occurs in the insulating layer, causing deformation after firing. However, there is a limit to satisfy both the reduction in thickness and the increase in thickness of the wiring conductor layer at the same time.

  Further, in order to form a vertical conductor such as a via conductor, a drilling process for forming a through hole by punching the green sheet is indispensable, and an additional process for the printing process for forming the wiring conductor layer It was.

As one means for suppressing the formation of a step due to the thickness of such a wiring conductor layer, an insulating layer is formed on a carrier film by applying a slurry made of a photocurable ceramic material, and a predetermined thickness is applied to the insulating layer. An opening is formed by exposing and developing the pattern, and a conductive paste is filled in the opening. Further, in Patent Document 4, a multilayer substrate without a step due to a conductor is formed on the surface by repeating the formation of a photocurable ceramic insulating layer, exposure, development, and filling of a conductor paste in the same manner as described above. Proposed.
JP 2002-185147 A JP 2002-290053 A JP-A-11-97854 JP-A-9-181450

  However, even in the case of providing a high dielectric constant layer or a magnetic layer, the method of forming a high dielectric constant green sheet or magnetic green sheet as in Patent Documents 1 and 2 has a high dielectric constant for all the specific layers of the multilayer circuit board. For example, since the dielectric constant is increased to a portion that is not necessary other than the portion where the capacitor is formed, the wiring conductor layer cannot be formed, and the circuit design is greatly restricted. There was a problem that. Even when a dielectric layer and an electrode layer are alternately laminated on the surface of an insulating green sheet to form a capacitor, the surface of the multilayer wiring board depends on the thickness of the capacitor itself laminated on the green sheet. There was a problem that the flatness of the glass was impaired.

  Further, when filling the recess with a high dielectric constant material paste or a magnetic material paste as in Patent Document 3, since the ceramic paste contains a solvent or the like, the ceramic green sheet is dried after the paste is dried. Steps are likely to occur between the surface and the paste filling surface, and as a result, there are problems such as poor stacking when a multilayer structure is formed. In addition, since the ceramic paste filling portion and the ceramic green sheet have different molding densities, it is difficult to make the firing shrinkage ratios coincide with each other. As a result, there is a problem that voids are generated in the joint portion.

  In addition, according to the method described in Patent Document 4, it is substantially necessary to sequentially form the circuits layer by layer, that is, the number of processes is very large and the processes cannot be performed in parallel. For this reason, it takes a long time to manufacture. In addition, when filling the opening with the conductive paste, it is necessary to accurately align the predetermined screen and the opening. In addition, when filling the conductor paste into the opening, filling of the paste into the through hole for forming a pattern with a small diameter such as a via or a small line width tends to be insufficient, and a nest that is not filled with paste is formed in the through hole. There was also a problem such as being easy to be done.

  Accordingly, the present invention provides a composite sheet in which a functional ceramic component and an insulating layer can be integrated and thinned, and the functional ceramic component is easily formed at an arbitrary location, and a method for manufacturing the same. With the goal. Also, a laminate capable of simultaneously satisfying the increase in thickness of the insulating layer and the wiring conductor layer by using such a composite sheet, and forming a three-dimensional circuit by a planar conductor and a vertical conductor by a simple method; An object of the present invention is to provide a manufacturing method thereof and a laminated part using the manufacturing method.

  The composite sheet of the present invention is characterized in that a functional ceramic component is embedded in a part of an insulating ceramic layer containing at least a ceramic material and a polymer material so as to penetrate the insulating ceramic layer. To do. In particular, it is desirable that the insulating ceramic layer and the functional ceramic component have a thickness of 100 μm or less, and the difference in thickness is 20% or less of the thickness of the insulating ceramic layer. Furthermore, the insulating ceramic layer contains at least a photocurable monomer and a photopolymerization initiator. The functional ceramic component is made of at least one of a ceramic resistance element, a ceramic capacitor, and a ceramic inductor, and the functional ceramic component is made of a green body. Furthermore, a conductor layer may be embedded in a part of the insulating ceramic layer so as to penetrate the insulating ceramic layer.

  In addition, as a method of manufacturing such a composite sheet, (a) a step of forming a conductive layer of a predetermined pattern on the surface of a light transmissive carrier film and placing a functional ceramic component; (b) the function A photocuring slurry containing at least a photocurable monomer, a photopolymerization initiator, and a ceramic material is applied on the carrier film on which the functional ceramic component is placed to a thickness equal to or greater than the thickness of the functional ceramic component. A step of forming a photocurable ceramic layer, (c) a step of irradiating light from the back surface of the carrier film and photocuring a region of the irradiated photocurable ceramic layer, and (d) a developer. By adding and solubilizing and removing the non-cured portion including the surface of the functional ceramic component of the photo-curable ceramic layer. Characterized by comprising the step of producing a composite sheet sexual ceramic component is embedded, the. Moreover, you may comprise the process of peeling the said composite sheet from the said carrier film after the said (d) process. The functional ceramic component and the photocurable ceramic layer in which the functional ceramic component is embedded are both 100 μm or less in thickness.

  In the laminate of the present invention, the functional ceramic component having substantially the same thickness as the insulating ceramic layer is formed on a part of the insulating ceramic layer containing at least the ceramic material and the polymer material. A part of the insulating ceramic layer containing the first composite sheet formed through the insulating ceramic layer, at least the ceramic material, and the polymer material is substantially the same as the insulating ceramic layer. A conductive layer having a thickness is formed by laminating a second composite sheet formed by penetrating the insulating ceramic layer. The thickness of the functional ceramic component and the insulating ceramic layer in which the functional ceramic component is embedded is desirably 100 μm or less.

  In addition, as a manufacturing method of the laminated body, (1a) a step of forming a conductive layer of a predetermined pattern on the surface of the light transmissive carrier film and placing a functional ceramic component; (1b) the functionality A photocuring slurry containing at least a photocurable monomer, a photopolymerization initiator, and a ceramic material is applied on a carrier film on which the ceramic component is placed to a thickness greater than the thickness of the functional ceramic component. A step of forming a photocurable ceramic layer, (1c) a step of irradiating light from the back surface of the carrier film, and photocuring a region of the irradiated photocurable ceramic layer, and (1d) a developer. By applying and solubilizing and removing the non-hardened part including the surface of the functional ceramic part of the photocurable ceramic layer, it functions in the photocurable ceramic layer. A step of producing a composite sheet in which ceramic parts are embedded, (2a) a step of forming a conductor layer of a predetermined pattern on the surface of a light-transmissive carrier film, and (2b) on the carrier film on which the conductor layer is formed. Applying a photocuring slurry containing at least a photocurable monomer, a photopolymerization initiator, and a ceramic material to a thickness equal to or greater than the thickness of the conductor layer to form a photocurable ceramic layer; 2c) a step of irradiating light from the back surface of the carrier film and photocuring the photocurable ceramic layer in a region other than the region where the conductor layer is formed; and (2d) applying the developer to the photocuring. The process of producing the 2nd composite sheet which comprises a photocurable ceramic layer and a conductor layer by solubilizing and removing the non-photohardening part containing the said conductor layer surface of a conductive ceramic layer Characterized by comprising the steps of laminating (e) and the first composite sheet, and said second composite sheet.

  The first composite sheet and the second composite sheet are either laminated after the carrier film is peeled off, or the second composite sheet is formed on the surface of the first composite sheet formed on the carrier film. After laminating the composite sheets, they may be laminated by peeling off the carrier film on the second composite sheet side.

  In addition, a sintered laminated body can be produced by firing the laminated body following the above-described steps.

  In the laminated component of the present invention, a plurality of insulating ceramic layers containing at least a ceramic material are laminated, and a functional ceramic component is embedded in at least a part of the insulating ceramic layer through the insulating ceramic layer. In addition, a conductive layer having a predetermined pattern is embedded in the insulating ceramic layer or the other insulating ceramic layer in which the functional ceramic component is embedded so as to penetrate the insulating ceramic layer.

  The functional ceramic component preferably has a thickness of 100 μm or less, and preferably has a three-dimensional conductor network formed by stacking the conductor layers. In addition, examples of the functional ceramic component include at least one of a ceramic resistance element, a ceramic capacitor, and a ceramic inductor.

  According to the present invention, by using the composite sheet in which the functional ceramic component is embedded, and laminating with another composite sheet, it is suitable for a multilayer circuit board in which the functional ceramic component is built in an arbitrary place. A laminate can be produced.

  In addition, since the functional ceramic parts are embedded with the same thickness as the insulating ceramic layer, there are no steps even if they are stacked, causing delamination, deformation due to excessive pressure, etc. It is possible to easily reduce the thickness of the insulating layer between conductor layers and increase the thickness of the conductor layer, and functional ceramics such as ceramic resistance elements, ceramic capacitors, and ceramic inductors. Components can be formed at any location with high accuracy.

  Further, by embedding a conductor layer in the composite sheet and laminating the composite sheet so that the conductor layer is laminated on the upper side, it is possible to insert 3 into the laminated body without filling the conductor paste into the conventional through-hole. A dimensional conductor network can be formed.

  Further, in the method for producing the composite sheet of the present invention, in forming the insulating ceramic layer, the functional ceramic component formed on the carrier film or the conductor layer itself is used as a mask, and the entire surface of the photocurable ceramic layer is applied. Because it can be formed by full exposure from the back side of the carrier film, it is not necessary to use a mask, etc., and it is a composite comprising a photocurable ceramic insulating layer and a functional ceramic component or conductor layer easily and inexpensively. A sheet can be easily produced.

  Moreover, since the production of such a composite sheet can be produced in parallel for each layer, if a composite sheet having the required number of layers is produced, and then laminated together and fired, The process can be shortened.

  FIG. 1 shows (a) a schematic perspective view and (b) a schematic cross-sectional view of a ceramic multilayer circuit board as an example of a laminated component in the present invention.

  According to the ceramic multilayer circuit board 1 of FIG. 1, the wiring conductor layer 3 serving as a planar conductor is formed on the front surface, the back surface, and the inside of the insulating substrate 2 made of a ceramic sintered body. A chip component 4 such as an inductor, a resistor, or a capacitor is mounted on the wiring conductor layer 3 formed on the surface by solder. A functional ceramic component 6 is embedded and formed in the insulating substrate 2. For example, in FIG. 1, a ceramic capacitor 6 is formed, and wiring conductor layers 7 and 7 are formed on the upper and lower surfaces thereof, and are electrically connected to the electrode 6 a of the ceramic capacitor 6. The wiring conductor layer 3 on the back surface functions as a terminal electrode for mounting on a mother board or the like. In addition, a via conductor 5 that connects the wiring conductor layers 3 that form the planar conductor is formed inside the insulating substrate 2.

  The ceramic multilayer circuit board 1 according to the present invention includes a composite A in which a functional ceramic component 6 is embedded and formed in a part of an insulating ceramic layer 2a having a thickness of 100 μm or less, through the insulating ceramic layer 2a, A wiring conductor layer 3 is formed in a part of the insulating ceramic layer 2b having a thickness of 50 μm or less by a laminated body with the composite B that is embedded and formed through the insulating ceramic layer 2b.

  More specifically, in the composite A, each of the insulating ceramic layer 2a and the functional ceramic component 6 is formed of a thin layer of 100 μm or less, particularly 10 to 50 μm, more preferably 10 to 30 μm. Desirably, the thickness difference between the insulating ceramic layer 2b and the functional ceramic component 6 is 20% or less, particularly 10% or less, more preferably 5% or less of the thickness of the insulating ceramic layer 2b. When the thickness difference is 5 μm or less, and further 3 μm or less, the occurrence of a step due to the individual thicknesses of the insulating ceramic layer 2b and the functional ceramic component 6 is suppressed.

  On the other hand, in the composite B, the wiring conductor layer 3 embedded in the insulating ceramic layer 2b forms a planar circuit by extending in the plane direction of the insulating ceramic layer 2b. Further, the vertical conductors 5 that connect the wiring conductor layers 3 in the vertical direction can be formed by partially stacking the wiring conductor layers 3 in the thickness direction. According to the composite B, it is desirable that the insulating ceramic layer 2b and the wiring conductor layer 3 are each formed of a thin layer of 10 to 50 μm, particularly 15 to 40 μm, more preferably 15 to 30 μm, The thickness difference between the insulating ceramic layer 2b and the wiring conductor layer 3 is 20% or less, particularly 10% or less, more preferably 5% or less of the thickness of the insulating ceramic layer 2b, or the thickness difference is 5 μm or less. Is 3 μm or less, the generation of steps due to the individual thicknesses of the insulating ceramic layer 2 b and the wiring conductor layer 3 is suppressed.

  According to the present invention, in the multilayer circuit board 1 for forming a desired circuit, the composite A and the composite B are 10 to 300 layers, particularly 30 to 200 layers, more preferably about 40 to 100 layers. It is formed by laminating with a composite.

The ceramic material for forming the insulating ceramic layer 2 includes (1) a ceramic material whose main component is Al ₂ O ₃ , AlN, Si ₃ N ₄ , SiC and having a firing temperature of 1100 ° C. or higher, and (2) at least Low-temperature fired ceramic material fired at 1100 ° C. or less, particularly 1050 ° C. or less, comprising a mixture of metal oxides containing SiO ₂ and alkaline earth metal oxides (RO) such as BaO, CaO, SrO, MgO, (3 ) At least one selected from the group of low-temperature fired ceramic materials which are fired at 1100 ° C. or lower, particularly 1050 ° C. or lower, consisting of glass powder or a mixture of glass powder and ceramic filler powder is selected.

Mixture or is (2) using, as a glass composition (3), at least include _{SiO 2, Al 2 O 3,} B 2 O 3, ZnO, PbO, alkaline earth metal oxides, alkali metal oxides Specifically, it contains at least one of these, and specifically includes SiO ₂ —B ₂ O ₃ —RO, SiO ₂ —BaO—Al ₂ O ₃ —RO, SiO ₂ —B ₂ O. Examples include _3- Al ₂ O ₃ -RO, SiO ₂ -Al ₂ O ₃ -RO, and compositions obtained by blending these systems with ZnO, PbO, Pb, ZrO ₂ , TiO _{2 and the} like. In addition, the glass is an amorphous glass by baking treatment, and by baking treatment, alkali metal silicate, quartz, cristobalite, cordierite, mullite, enstatite, anorthite, serdian, spinel, garnite, Crystallized glass that precipitates at least one crystal of diopside, ilmenite, willemite, dolomite, petalite, and substituted derivatives thereof is used.

Further, as the ceramic filler in (3), Al ₂ O ₃ , SiO ₂ (quartz, cristobalite), forsterite, cordierite, mullite, ZrO ₂ , mullite, forsterite, enstatite, spinel, magnesia, AlN, Si Examples include at least one selected from the group of titanates such as ₃ N ₄ , SiC, MgTiO ₃ , and CaTiO _3, and it is desirable that the glass is mixed at a rate of 20 to 80% by mass with respect to the glass.

  In particular, the glass component and the ceramic filler component are mixed in a proportion of 10 to 90% by weight, particularly 50 to 80% by weight, and 10 to 90% by weight, particularly 20 to 50% by weight of the ceramic filler component. Preferably used.

  On the other hand, since the wiring conductor layer 3 is formed by simultaneous firing with the insulating ceramic layer 2, various combinations are made according to the firing temperature of the ceramic material forming the insulating ceramic layer 2. In the case of 1), a conductor material mainly containing at least one selected from the group consisting of tungsten, molybdenum, manganese and copper is preferably used. Moreover, it is good also as a mixture with copper etc. for resistance reduction.

  When the ceramic material is (2) or (3), a conductor material mainly containing at least one selected from the group consisting of copper, silver, gold, and aluminum is preferably used. The conductor material preferably contains a component constituting the ceramic material when co-firing with the ceramic material.

  The functional ceramic component 6 is variously changed depending on the purpose, but the insulating ceramic layer 2b and the functional ceramic component 6 are fired at substantially the same firing temperature.

For example, when the ceramic material of 1100 ° C. or higher, particularly 1200 ° C. or higher of (1) is used as the insulating ceramic layer 2b, the functional ceramic component 6 is composed of alumina, aluminum nitride, silicon nitride, forsterite, mullite, forsterite, Main component is at least one selected from the group of enstatite, silica, cordierite, titanate such as BaTiO ₃ and Fe ₂ O ₃ , and if necessary, lower dielectric constant, higher dielectric constant, magnetic It is desirable to add ceramics and metal components for forming into a body, and to use a ceramic material capable of being fired at the same firing temperature as the insulating ceramic layer 2b.

On the other hand, when the ceramic material of (2) and (3) of 1100 ° C. or lower, particularly 1050 ° C. or lower is used as the insulating ceramic layer 2b, various functionalities are available for the low-temperature firing composition forming the insulating ceramic layer. Can be selected and added. For example, when forming a low dielectric constant material, the low dielectric constant glass or glass ceramic material containing at least one filler selected from the group of low dielectric constant silica, cordierite, and enstatite may be used. desirable. Moreover, when forming a high dielectric constant ceramic layer, it is desirable to form with a glass ceramic material containing titanates such as BaTiO ₃ and LaTiO ₃ as fillers.

Further, when the functional ceramic component 6 is formed of a magnetic material, it is desirable to form the functional ceramic component 6 using a glass ceramic material containing at least a compound containing an iron group element such as Fe, Co, or Ni. Further, in the case of forming with a resistance material, it is desirable to form with a glass ceramic material to which ReO ₂ or a metal component is added.

  In addition, it is desirable that the functional ceramic component itself is capable of forming one electronic component after firing. For example, a capacitor component having a high dielectric layer and a pair of electrodes sandwiching the high dielectric layer, a multilayer capacitor component in which high dielectric layers and electrode layers are alternately arranged, and a resistor element having a resistor layer and a pair of electrodes Various electronic components such as an inductor element in which a multilayer circuit is formed in a multilayer dielectric layer and an inductor is formed, and an antenna element in which an antenna circuit is formed in a multilayer dielectric layer are used.

  In forming a multilayer component such as the ceramic multilayer circuit board 1 as described above, according to the present invention, first, an insulating ceramic containing at least a ceramic material and a polymer material as shown in FIG. A composite sheet in which a functional ceramic component (hereinafter simply referred to as a functional ceramic component) 6a is formed in part of the layer 2a, and a conductor layer 3a is formed through the insulating ceramic layer 2a as necessary. a is produced.

  Further, according to the present invention, a conductor is formed on a part of the insulating ceramic layer 2a containing the composite sheet a and at least a ceramic material and a polymer material as shown in FIG. A composite sheet b in which the layer 3a is formed so as to penetrate the insulating ceramic layer 2a is produced.

  The thickness of the composite sheet a is substantially the same as the thickness of the functional ceramic component 6a, and is a thickness necessary as a component for imparting a function. However, the thickness difference between the insulating ceramic layer 2a and the functional ceramic component 6a is 20% or less of the thickness of the insulating ceramic layer 2a, particularly 10% or less, more preferably 5% or less, or the thickness difference is 5 μm. Hereinafter, the occurrence of a step due to the individual thicknesses of the insulating ceramic layer 2a and the functional ceramic component 6a is further suppressed by being 3 μm or less.

  On the other hand, in the composite sheet b, it is desirable that the insulating ceramic layer 2a and the conductor layer 3a have a thickness of 10 to 50 μm, particularly 15 to 40 μm, more preferably 15 to 30 μm. The thickness difference between the ceramic layer 2a and the conductor layer 3a is 20% or less of the thickness of the insulating ceramic layer 2a, particularly 10% or less, more preferably 5% or less, or the thickness difference is 5 μm or less, further 3 μm or less. As a result, the occurrence of steps due to the individual thicknesses of the insulating ceramic layer 2a and the conductor layer 3a is suppressed.

  In producing the composite sheets a and b, first, in order to form the insulating ceramic layer 2a, a photocuring slurry containing at least a photocurable monomer and the above-described ceramic material is prepared. In preparing the slurry, desirably, the ceramic material is prepared by mixing a photocurable monomer, a photopolymerization initiator, an organic binder, and a plasticizer in an organic solvent and kneading with a ball mill.

  Examples of the photocuring component include a photocurable monomer and a photopolymerization initiator. As the photocurable monomer, it is desirable that the monomer is excellent in thermal decomposability in order to cope with a low-temperature and short-time baking process. In addition, the photo-curable monomer needs to be photopolymerized by exposure after application and drying of the slip material, and can form free radicals and chain-growth addition polymerization, and has a secondary or tertiary carbon. Preferred examples include alkyl acrylates such as butyl acrylate having at least one polymerizable ethylene group, and alkyl methacrylates corresponding thereto. In addition, polyethylene glycol diacrylates such as tetraethylene glycol diacrylate and methacrylates corresponding thereto are also effective. Examples of the photopolymerization initiator include benzophenones and acyloin ester compounds.

  In addition, the organic binder is desired to have good thermal decomposability like the photo-curable monomer, and at the same time, it determines the viscosity of the slip, so it is necessary to consider the wettability with the solid content. is there. According to the present invention, an ethylenically unsaturated compound having a carboxyl group and an alcoholic hydroxyl group such as an acrylic acid or methacrylic acid polymer is preferred.

  Examples of the organic solvent include at least one selected from the group consisting of ethyl carbitol acetate, butyl cellosolve, and 3 methoxybutyl acetate.

  The content of each component is 5 to 20 parts by mass of a photocurable monomer and a photopolymerization initiator, 10 to 40 parts by mass of an organic binder, 1 to 5 parts by mass of a plasticizer, and an organic solvent per 100 parts by mass of the ceramic powder. A ratio of 50 to 100 parts by mass is appropriate.

  Next, a conductor paste for forming the conductor layer 3a is prepared. The conductive paste is an inorganic component obtained by adding a ceramic material to the powder of the conductive material having an average particle diameter of about 1 to 3 μm, if necessary, and an organic binder such as ethyl cellulose and acrylic resin, and further dibutyl phthalate, A suitable solvent such as α-terpineol, butyl carbitol, 2,2,4-trimethyl-3,3-pentadiol monoisobutyrate is mixed and homogeneously kneaded by a three roll mill or the like.

  The content of each component is 5 to 20 parts by mass of a photocurable monomer and a photopolymerization initiator, 10 to 30 parts by mass of an organic binder, 1 to 5 parts by mass of a plasticizer, and an organic solvent per 100 parts by mass of the ceramic powder. A ratio of 50 to 100 parts by mass is appropriate.

  The functional ceramic component 6a is a conventionally known ceramic electronic component. As an example of a ceramic multilayer capacitor, a ceramic dielectric layer having an electrode pattern formed thereon is laminated, an internal electrode is exposed on the end face, and an external electrode is printed on the end face.

  Next, a composite sheet is formed by the following steps using the above-mentioned photocuring slurry, conductor paste, and functional ceramic component.

  First, as shown in FIG. 3A, a functional ceramic component 12 is placed on a light transmissive carrier film 10 made of a resin film or the like.

  Next, as shown in FIG. 3 (b), the photocuring slurry is applied to a thickness equal to or greater than the thickness of the functional ceramic component 12 by, for example, a doctor blade method, and applied to the entire surface with a predetermined thickness. A photocurable ceramic layer 13 is formed.

  And as shown in FIG.3 (c), it exposes from the back surface of the carrier film 10 using an ultrahigh pressure mercury lamp as a light source, for example. By this exposure, the photocurable ceramic layer 13 in a region other than the place of the functional ceramic component 12 is photocured. In this exposure step, the photocurable ceramic layer 13 undergoes a photopolymerization reaction from the back surface to a certain thickness depending on the amount of light irradiated on the photocurable ceramic layer 13a in a region other than the functional ceramic component 12 placement. Although the insolubilized portion is formed, since the functional ceramic component 12 does not pass ultraviolet rays, the photocurable ceramic layer 13b formed on the functional ceramic component 12 undergoes a photopolymerization reaction of a photocurable monomer. There will be no solubilized part. In addition, the exposure amount at this time is desirably adjusted so that the thickness of the insolubilized portion is substantially the same as the thickness of the functional ceramic component 12.

  Thereafter, the entire photocurable ceramic layer 13 is developed. The development treatment is to remove the solubilized portion of the photocurable ceramic layer 13 with a developer. Specifically, for example, spray development, washing, and drying are performed using a triethanolamine aqueous solution as the developer. By this treatment, as shown in FIG. 3D, a composite sheet a in which the functional ceramic component 12 and the photocurable ceramic layer 13 are integrated with substantially the same thickness is formed on the carrier film 10. The

  In addition, the composite sheet a simple substance as shown to Fig.2 (a) can be obtained by peeling the composite sheet a from the carrier film 10. FIG.

  Also, the composite sheet b of FIG. 2B is exactly the same as the above except that in the method of manufacturing the composite sheet a, the conductor layer 11 is formed by printing and applying a conductor paste instead of the functional ceramic component 12. It can be manufactured through similar steps.

  Of course, it is also possible to form a conductor sheet 11 and a functional ceramic layer 12 on the surface of the carrier film 10 and to produce a composite sheet having the conductor layer 11 and the functional ceramic layer 12 together through the same process as described above. it can.

  Next, a method for producing a laminated component such as the ceramic multilayer circuit board of FIG. 1 using this composite sheet a will be described. First, according to FIGS. 3 (a) to 3 (d), a functional ceramic component. A plurality of composite sheets a on which 12 and the photocurable ceramic layer 13 are formed are produced. Moreover, the some composite sheet b1-b12 in which the photocurable ceramic layer 13 and the conductor layer 11 of the predetermined pattern were formed is produced.

  And as shown to Fig.4 (a), the laminated body 14 is formed by superposing | stacking and crimping | bonding together these composite sheets a and b1-b12, aligning. In addition, it is desirable to perform the pressure bonding while applying a temperature equal to or higher than the glass transition point of the organic binder in the composite sheet a. Further, an organic adhesive may be applied between the composite sheets for pressure bonding.

  In addition, when laminating all at once, the carrier film 10 may be peeled off and laminated, but considering the handling of the lowermost surface and the uppermost surface during crimping, only the lowermost surface and the uppermost surface are removed from the carrier film 10. As shown in FIG. 4A without peeling off, the laminated body 14 as shown in FIG. 4B can be formed by peeling off the carrier film 10 after lamination and pressure bonding.

  The laminated body 14 is fired at a predetermined temperature to sinter the functional ceramic component 12 together with the photocurable ceramic layer and the conductor layer 11, thereby forming a three-dimensional circuit by the conductor layer 11. In addition, a laminated part including the functional ceramic part 12 can be formed. In firing, the produced laminate 14 is burned away in an organic binder and photocurable monomer contained in the molded body, and the firing process is performed in an inert atmosphere such as nitrogen in the firing step. Then, the used insulating ceramic material, functional ceramic component and conductor material are fired at a temperature at which they can be sufficiently fired, and the ceramic layer is densified to a relative density of 95% or more.

  Further, as another method for manufacturing a laminated component, as shown in FIGS. 5A, 5B, and 5C, the surface of the carrier film 10 is formed on the surface of the composite sheet b12 formed on the surface of the carrier film 10. The composite sheet b11 formed in the above is inverted and laminated and pressure-bonded, and the carrier film 10 on the composite sheet b11 side is peeled off.

  Next, as shown in FIG. 5 (d), the composite sheet b10 formed on the surface of the carrier film 10 in the same manner is reversed and laminated and pressure-bonded to the surface of the composite sheet b11, so that the carrier on the composite sheet b10 side is obtained. The film 10 is peeled off. By repeating this, a desired total number of stacked bodies 14 can be formed. Thereafter, this laminated body 14 is fired in the same manner as described above to produce a laminated component.

  Further, as necessary, as a surface treatment, a thick film resistance film or a thick film protective film is printed / baked on the substrate surface, a plating process, and an electronic component 4 including an IC chip is mounted.

  The surface conductor layer 3 may be printed and dried on the surface of the fired laminate 14 and baked in a predetermined atmosphere.

  In addition, on the surface of the surface conductor layer 3 and the terminal electrode 9 formed on the surface of the ceramic multilayer circuit board, a plating layer of nickel, gold or the like has a thickness of 1 to 3 μm in order to improve wettability with solder. It is formed.

  Further, as shown in FIG. 1B, a photocurable ceramic layer 13 and a conductor layer having a predetermined pattern are formed on at least one surface of the composite sheet a including the functional ceramic component 6 formed in the insulating substrate 2. By laminating the composite sheets b3 and b4 on which 11 is formed, the circuit formed of the conductor layer 11 and the functional ceramic component can be electrically connected.

  First, a conductor paste was printed on a light transmissive carrier film made of PET (polyethyl terephthalate) having a thickness of 100 μm by a screen printing method to form a conductor layer to be a wiring conductor layer having a thickness of 20 μm. In addition, the conductor paste used was a barium borosilicate glass powder, cellulose, and an organic solvent added to Ag powder and mixed by a three-roll mill.

Subsequently, a chip capacitor having a thickness of 25 μm before firing was placed on the carrier film. The chip capacitor is composed of a laminated body in which five dielectric layers of 4 μm thickness made of BaTiO ₃ based dielectric material and four electrode layers of 2 μm thickness are alternately laminated.

  Next, the photosensitive slurry was applied and dried on the chip capacitor by a doctor blade method to form a photocurable ceramic layer so that the thickness after drying in a place where no chip capacitor was present was 30 μm.

  The photosensitive slurry is 100 parts by mass of ceramic raw material powder, 8 parts by mass of photocurable monomer (polyoxyethylated trimethylolpropane triacrylate), 35 parts by mass of organic binder (alkyl methacrylate), and 3 parts by mass of plasticizer. And 20 parts by mass of an organic solvent (ethyl carbitol acetate) and kneaded with a ball mill.

The ceramic raw material powder is a ceramic material having a composition of SiO ₂ —Al ₂ O ₃ —MgO—ZnO—BaO—B ₂ O ₃ glass powder 82% by mass and SiO ₂ 18% by mass (relative dielectric constant: 6.5). Was used.

Next, the entire surface was exposed from the back side of the carrier film to the back side of the photocurable ceramic layer for 2 seconds using an ultrahigh pressure mercury lamp (illuminance 30 mW / cm ² ) as a light source. Then, spray development was performed for 30 seconds using a triethanolamine aqueous solution having a dilution concentration of 2.5% as a developer. Thereafter, the film was dried after being washed with pure water after development.

  In this way, the completed photocurable ceramic layer has the melted portion on the chip capacitor removed by development to expose the chip capacitor. As a result, the photocurable ceramic layer having a thickness of 25 μm, the chip capacitor having a thickness of 25 μm, Was able to produce a composite sheet a.

  In the same manner as described above, a total of 50 composite sheets b in which a conductor layer having a thickness of 20 μm and a photocurable ceramic layer having a thickness of 20 μm were integrated were produced.

  From the composite sheet produced as described above, the carrier film was peeled off, and lamination was performed while positioning in order. Thereafter, using a press machine, pressing was performed for 5 minutes at a pressing pressure of 1 ton and a temperature of 60 ° C., and the laminate was pressure bonded.

  Thereafter, the binder removal treatment was performed in the atmosphere at 300 ° C. for 4 hours, and then the substrate was baked in the atmosphere at 900 ° C. for 6 hours to produce a ceramic multilayer circuit board with a built-in chip capacitor.

  The produced multilayer circuit board had no step due to the thickness of the conductor layer or the chip capacitor itself, and there was no delamination between layers. In connecting the wiring conductor layers, via conductors were formed by laminating three or more conductor layers in the vertical direction. However, there was no problem with electrical connection in a circuit including the via conductors. In addition, no nests were found in the conductor layer, and the chip capacitor also exhibited the desired characteristics.

  According to Example 1, a composite sheet having a total of 70 layers for forming an internal wiring conductor layer, a surface wiring conductor layer, a via conductor, and a functional ceramic component was prepared.

  According to the method of FIG. 5, first, the composite sheet for via conductors was inverted together with the carrier film on the composite sheet for electrodes, and the composite sheets were brought into contact with each other and placed while performing alignment. Subsequently, using a press machine, pressing was performed for 1 minute at a pressing pressure of 1 ton and a temperature of 60 ° C., and the composite sheet for the via conductor and the composite sheet for the via conductor were pressure-bonded to each other. The carrier film on the sheet side was peeled off.

  Subsequently, another composite sheet for via conductors, a composite sheet for internal wiring conductor layers, a composite sheet for surface wiring conductor layers, and a composite sheet for functional ceramic parts are sequentially reversed in the same manner and mounted while performing alignment. And then sequentially crimped using a press.

  Thereafter, the binder removal treatment was performed in the atmosphere at 300 ° C. for 4 hours, and then the substrate was baked in the atmosphere at 900 ° C. for 6 hours to produce a multilayer circuit board.

  The produced multilayer circuit board had no step due to the thickness of the conductor layer or the chip capacitor itself, and there was no delamination between the insulating layers. In connecting the wiring conductor layers, via conductors were formed by laminating three or more conductor layers in the vertical direction. However, there was no problem with electrical connection in a circuit including the via conductors. In addition, no nests were found in the conductor layer. The chip capacitor also exhibited the desired characteristics.

As an example of the multilayer component of the present invention, (a) a schematic perspective view and (b) a schematic sectional view of a ceramic multilayer circuit board are shown. It is a schematic sectional drawing for demonstrating the composite sheet of this invention. It is process drawing for demonstrating the preparation methods of the composite sheet of this invention. It is process drawing for demonstrating the method of producing the laminated component of this invention. It is process drawing for demonstrating the other method of producing the laminated component of this invention.

Explanation of symbols

A Composite sheet 1 Ceramic multilayer circuit board 2 Insulating substrate 2a, 2b Ceramic layer 3 Wiring conductor layer 4 Chip component 5 Via conductor 6 Functional ceramic component 11, 3a Conductive layer 12, 6a Functional ceramic component 13, 2a Ceramic layer

Claims (19)

A composite sheet comprising a functional ceramic component embedded in a part of an insulating ceramic layer containing at least a ceramic material and a polymer material so as to penetrate the insulating ceramic layer. 2. The composite according to claim 1, wherein the insulating ceramic layer and the functional ceramic component each have a thickness of 100 μm or less, and a thickness difference thereof is 20% or less of the thickness of the insulating ceramic layer. Sheet. The composite sheet according to claim 1 or 2, wherein the insulating ceramic layer contains at least a photocurable monomer and a photopolymerization initiator. The composite sheet according to any one of claims 1 to 3, wherein the functional ceramic component is at least one of a ceramic resistance element, a ceramic capacitor, a ceramic inductor, and an antenna element. The composite sheet according to any one of claims 1 to 4, wherein the functional ceramic component comprises an unfired body. The composite sheet according to any one of claims 1 to 5, wherein a conductor layer is formed in a part of the insulating ceramic layer so as to penetrate the insulating ceramic layer. (A) placing a functional ceramic component on the surface of a light transmissive carrier film;
(B) A photocuring slurry containing at least a photocurable monomer, a photopolymerization initiator, and a ceramic material on the carrier film on which the functional ceramic component is placed is equal to or greater than the thickness of the functional ceramic component. Applying to a thickness to form a photocurable ceramic layer;
(C) irradiating light from the back surface of the carrier film and photocuring a region of the irradiated photocurable ceramic layer;
(D) The functional ceramic component is embedded in the photocurable ceramic layer by applying a developer and solubilizing and removing the non-cured portion including the surface of the functional ceramic component of the photocurable ceramic layer. Producing a composite sheet,
A method for producing a composite sheet, comprising: After the step (d),
(E) The manufacturing method of the composite sheet of Claim 7 which comprises the process of peeling the said composite sheet from the said carrier film. 9. The method for producing a composite sheet according to claim 7, wherein the functional ceramic component and the photocurable ceramic layer in which the functional ceramic component is embedded have a thickness of 100 μm or less. A functional ceramic component having substantially the same thickness as the insulating ceramic layer is formed in a part of the insulating ceramic layer containing at least the ceramic material and the polymer material so as to penetrate the insulating ceramic layer. A first composite sheet,
A conductor layer having substantially the same thickness as the insulating ceramic layer is formed on a part of the insulating ceramic layer containing at least the ceramic material and the polymer material so as to penetrate the insulating ceramic layer. A second composite sheet,
A laminate obtained by laminating layers. The laminate according to claim 10, wherein a thickness of the functional ceramic component and an insulating ceramic layer in which the functional ceramic component is embedded is 100 μm or less. (1a) placing a functional ceramic component on the surface of a carrier film capable of transmitting light;
(1b) On the carrier film on which the functional ceramic component is placed, a photocurable slurry containing at least a photocurable monomer, a photopolymerization initiator, and a ceramic material is larger than the thickness of the functional ceramic component. Applying to a thickness to form a photocurable ceramic layer;
(1c) irradiating light from the back surface of the carrier film and photocuring the region of the irradiated photocurable ceramic layer;
(1d) The functional ceramic component is embedded in the photocurable ceramic layer by applying a developer and solubilizing and removing the non-cured portion including the surface of the functional ceramic component of the photocurable ceramic layer. Producing a composite sheet,
(2a) forming a conductor layer having a predetermined pattern on the surface of the carrier film capable of transmitting light;
(2b) A photocuring slurry containing at least a photocurable monomer, a photopolymerization initiator, and a ceramic material is applied on the carrier film on which the conductor layer is formed to a thickness equal to or greater than the thickness of the conductor layer. Forming a photocurable ceramic layer,
(2c) irradiating light from the back surface of the carrier film and photocuring the photocurable ceramic layer in a region other than the region where the conductor layer is formed;
(2d) A second solution comprising a photocurable ceramic layer and a conductor layer by applying a developer and solubilizing and removing the non-photocured portion including the surface of the conductor layer of the photocurable ceramic layer. Producing a composite sheet;
(E) The manufacturing method of the laminated body characterized by including the process of laminating | stacking a said 1st composite sheet and a said 2nd composite sheet. The method for producing a laminate according to claim 12, wherein the first composite sheet and the second composite sheet are both laminated after the carrier film is peeled off. 13. The laminated body according to claim 12, wherein after the second composite sheet is laminated on the surface of the first composite sheet formed on the carrier film, the carrier film on the second composite sheet side is peeled off. Method. The manufacturing method of the laminated body in any one of Claim 12 thru | or 14 which comprises the process of baking the said laminated body. A plurality of insulating ceramic layers containing at least a ceramic material are laminated, and a functional ceramic component is embedded in at least a part of the insulating ceramic layer so as to penetrate the insulating ceramic layer. A laminated part, wherein a conductive layer having a predetermined pattern is embedded in an insulating ceramic layer or other insulating ceramic layer in which the part is embedded, through the insulating ceramic layer. The multilayer component according to claim 16, wherein the thickness of the functional ceramic component is 100 µm or less. The multilayer component according to claim 16 or 17, wherein a three-dimensional conductor network is formed by laminating an insulating ceramic layer in which the conductor layer is embedded. The multilayer component according to any one of claims 16 to 18, wherein the functional ceramic component is at least one of a ceramic resistance element, a ceramic capacitor, and a ceramic inductor.

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