JP4191675B2 - Manufacturing method of ceramic green sheet - Google Patents

Description

  The present invention relates to a method for producing a ceramic green sheet used for electronic parts, particularly electronic parts such as those made of a so-called laminated ceramic formed by laminating ceramic sheets. Specific examples of the multilayer ceramic electronic component described herein include a multilayer ceramic capacitor, a multilayer ceramic inductor, an LC composite component incorporating these, an EMC-related component, and the like.

  In recent years, with the miniaturization and rapid spread of electronic devices such as mobile phones, there is a need for higher-density mounting and higher performance for electronic components used therefor. In particular, multilayer ceramic electronic components used as passive elements are required to be reduced in size and functionality by thinning and multilayering in order to meet such demands, and a manufacturing method capable of meeting such demands. Is required.

  Further, in accordance with these requirements, a method for forming a ceramic green sheet in a multilayer ceramic electronic component formed by laminating ceramic green sheets has been studied.

  Due to recent demands for miniaturization, high performance (high integration), etc. in multilayer electronic components, fine patterning, that is, miniaturization of through holes, has been progressing in producing ceramic green sheets. Furthermore, instead of punching with a die or a pin, and a conventional through hole processing method with a laser or the like, a technique of forming through holes with a minute diameter and a minute pitch by a photolithography technique has been introduced.

  For this purpose, there has been reported an example of forming a resist pattern in which a post having a reverse pattern is formed with a resist instead of first forming a through-hole in processing of a ceramic green sheet. However, if the resist posts are covered with slurry, the positive cannot be removed and the through holes cannot be formed. Furthermore, the photosensitive binder is expensive, and further improvements in production cost and the like are desired.

  For example, Patent Document 1 discloses a method for forming a resist pattern, using a mask in which a first positive resist film is formed on the surface of a material for forming a resist pattern, and a pattern opposite to the target pattern is formed. The first positive resist film is exposed, developed to form a first resist pattern, and the entire surface is exposed, and then a second portion of the surface of the material where the first resist pattern is not formed. A resist pattern forming method is characterized in that the first resist pattern is removed by forming a resist film and then developing the resist film.

  The present invention aims to form a fine resist pattern and is a method that employs two positive resist film formations, but is premised on that the post of the first resist pattern does not fall off the formation surface. . In the second embodiment of Patent Document 1, the second mask alignment and exposure are still performed, and the described problem has not been solved.

  Further, Patent Document 2 discloses a ceramic multilayer substrate and a method for manufacturing the same, and an unsintered material that is not sintered at the sintering temperature of the laminate on both upper and lower surfaces of a laminate obtained by laminating a plurality of ceramic green sheets. A ceramic multilayer substrate comprising a ceramic green sheet containing and fired under pressure, wherein a via and wiring are formed on the dried photosensitive ceramic green sheet or photosensitive ceramic paste, and the insulating layer is fired at least. A ceramic multilayer substrate comprising a single layer is provided.

  The present invention provides a ceramic multilayer substrate capable of forming vias with high accuracy and high efficiency, and capable of forming micro diameters and pitches, and forming holes with a micro diameter of 50 μm in a t = 100 μm sheet. , Vias with a minimum diameter of 30 μm and a minimum pitch of 0.1 mm are formed.

However, in the present invention, it is limited to a ceramic material that is transparent to light to be exposed, and since it is expensive because only a photosensitive green sheet is used, a versatile method for producing a ceramic green sheet is provided. It is not provided.
Japanese Patent No. 3243904 Japanese Patent Application Laid-Open No. 11-195874

  In the conventional method for producing a ceramic green sheet, a photosensitive slurry is frequently used, and since this photosensitive slurry is expensive, there is a problem in terms of the production cost of the ceramic green sheet. Furthermore, there is a problem that the resist post is more likely to drop off than the substrate release surface.

  That is, since the surface of a base material such as a PET film that has been subjected to release treatment on the premise of green sheet peeling or transfer and lamination is generally in a state in which the formed material is easy to peel off, Even when trying to form a post-like formation on a substrate, the adhesion between the substrate and the patterned post is poor, and the patterned post eventually falls off the substrate and is stable. Forming a substrate with patterned posts has not been easy.

  As a result of earnestly examining the problems, the present inventors have found a method of forming a punch pattern or a through hole in a ceramic green sheet by applying a normal dielectric slurry or magnetic slurry without using a photosensitive slurry. I found it.

  That is, without using an expensive photosensitive binder (photosensitive slurry), a pattern formed product corresponding to a punched pattern or a through hole is formed by photolithography using a positive resist, and then the slurry is applied and covered on the entire surface, By forming a repellent layer (ceramic slurry repellent layer) on the upper surface of the pattern formation with a positive resist, the upper surface of the pattern formation is not covered with the slurry due to the repelling action, so that the pattern can be removed. It is what I found. Further, a layer (adhesion layer) that adheres a resist pattern to be formed later to the substrate with a low-solubility alkali material that is well-suited on the substrate subjected to the release treatment, for example, slightly less soluble than the resist. After forming a resist pattern (post) on this adhesion layer and further forming a repellant layer on this post, an alkali-insoluble material layer is applied and formed, and then subjected to alkali dissolution treatment to form a resist pattern and By removing both adhesive layers of the resist pattern and processing through-holes, it is possible to form a patterned post even on a release-treated substrate, and to remove this later It was found that a through hole can be formed. Furthermore, it has also been found that, as the material of the alkali-insoluble material layer used in the method for processing the ceramic green sheet, for example, either a dielectric slurry or a magnetic slurry can be used.

  That is, according to the present invention, a pattern formation (post) corresponding to a blank pattern or a through hole is formed on a base material by photolithography of a positive resist (disappearing material). After forming a repellent layer on the top surface, for example, a ceramic slurry repellent layer, the ceramic slurry is applied and dried, and the positive resist (disappearing material), which is a pattern formation, is eliminated to form a pattern or through hole in the ceramic green sheet. This is a method for producing a ceramic green sheet.

  Furthermore, the present invention provides an adhesive layer (an alkali-low-solubility insulating layer or an alkali-soluble insulating layer) is formed on a release-treated substrate, and a positive resist (disappearing material) photolithography is performed to remove a pattern or pattern. A post corresponding to the through hole is formed, and a repellant layer, for example, a ceramic slurry repellant layer is formed on the upper surface of the formed post, and then applied to the slurry, dried, and then subjected to positive resist (disappearing material) and adhesion layer. It is also a method for producing a ceramic green sheet in which a punching pattern or a through hole is formed in the ceramic green sheet by a melting treatment.

  This slurry needs to be insoluble in alkali, but may be either a dielectric slurry or a magnetic slurry.

  The solution may be a weak alkaline solution when leaving a removal pattern, or a strong alkaline solution when dissolving the positive resist (disappearing material) and the adhesion layer.

  In the present invention, the adhesion layer is used to enhance the adhesion between the base material and the disappearing material, and therefore the term “disappearing material adhesion layer” is used in this specification. Furthermore, the disappearing material adhesion layer is formed of an insulating material having a low alkali solubility, a disappearing material having a low alkali solubility, an alkali-soluble disappearing material, or an alkali-soluble material depending on the desired pattern processing and the desired ceramic green sheet. It can be optionally used from any of the insulating materials before and after firing, or in a range that does not affect the properties.

  By adopting such a configuration, the present invention makes it possible to process a fine pattern or through hole by photolithography on a non-photosensitive green sheet, and does not use an expensive photosensitive binder. It is advantageous in terms of cost, and furthermore, the ceramic green sheet can be patterned with a familiar adhesion layer (alkali low-solubility insulating layer or alkali-soluble insulating layer) sandwiched on the PET base material. It is possible to achieve both the mold releasability of the sheet and the adhesion of the resist pattern, prevent the resist pattern from falling off the substrate surface, and in both cases of dielectric green sheets and magnetic green sheets Can be used, and can be used for a wide range of purposes.

  One embodiment of the present invention is a method for producing a ceramic green sheet for a multilayer electronic component in which an insulating material is formed on a substrate after forming a pattern with the disappearing material, and pattern grooves or through holes are formed by the disappearing treatment. And at least a step of forming a pattern of the disappearing material on the substrate, a step of forming a ceramic slurry repelling layer on the pattern of the disappearing material, and a pattern of the disappearing material on which the ceramic slurry repelling layer is formed. A method for producing a ceramic green sheet comprising: forming an insulator material on a member; and applying a disappearance treatment to the member on which the insulator material is formed.

  Another embodiment of the present invention is the production of a ceramic green sheet for a multilayer electronic component in which an insulating material is formed on a substrate after forming a pattern with the disappearing material, and pattern grooves or through holes are formed by the disappearing treatment. A method comprising: forming at least a disappearing material adhesion layer on a substrate; forming a pattern with a disappearing material on a member on which the disappearing material adhesion layer is formed; and a ceramic slurry on the pattern with the disappearing material A step of forming a repellent layer, a step of forming an insulator material on a member having a pattern of a disappearing material on which the ceramic slurry repellent layer is formed, a step of applying a disappearance treatment to the member on which the insulator material is formed, and It is a manufacturing method of the ceramic green sheet characterized by including.

  In still another embodiment of the present invention, the disappearing material is made of a photosensitive material, and after the disappearing material is formed on the base material or the disappearing material adhesion layer, a pattern of the disappearing material is formed by a photolithography method. The method for producing a ceramic green sheet according to the above, wherein the ceramic green sheet is formed.

  In still another embodiment of the present invention, the ceramic green sheet according to the above, wherein the thickness of the insulating material layer is formed substantially coincident with the height of the pattern of the disappearing material. It is a manufacturing method.

  Yet another embodiment of the present invention is the method for producing a ceramic green sheet according to the above, wherein the step of performing the disappearance treatment forms a penetration pattern according to the disappearance material pattern by a dissolution treatment. is there.

  Yet another embodiment of the present invention is the above-mentioned method for producing a ceramic green sheet, wherein the disappearing material adhesion layer is made of an insulator material.

  Yet another embodiment of the present invention is the method for producing a ceramic green sheet as described above, wherein the lost material adhesion layer is made of an alkali-soluble material.

  Another embodiment of the present invention is a laminated mold characterized in that it is formed by laminating, pressing, and firing a ceramic green sheet group including a ceramic green sheet obtained by the method for producing a ceramic green sheet described above. Ceramic electronic components.

  In the present invention, examples of the slurry repellent layer include compounds containing many C—H bonds such as paraffin, silicone resin compounds, and fluorine compounds having C—F bonds, when the solvent of the ceramic slurry is aqueous. There are also water- and oil-repellent perfluoroalkyl group-containing silicone compounds, fluorine compounds, etc., and materials that have a repelling effect suitable for solvents used in ceramic slurries, such as water-based and organic solvent-based materials, are appropriately selected and used It is preferable to do.

  Moreover, it is preferable that the contact angle of the ceramic slurry repellent layer and the ceramic slurry (solvent in the ceramic slurry) is an obtuse angle. By appropriately adjusting the effect of this, the ceramic slurry viscosity, the ceramic slurry coating thickness, etc., and repelling the ceramic slurry on the repellent layer, it becomes possible to form a space without the ceramic slurry above the repellent layer. (Repel effect).

  Examples of the method for forming the repellent layer on the pattern of the disappearing material include a printing method, a transfer method (using a transfer head, a transfer roll, etc.), an ink jet coating method, and the like.

  In addition, when the disappearing material adhesion layer is used, the disappearing material surface may be roughened during the surface and any step of pattern formation with the disappearing material (not shown). As a result, it becomes possible to further enhance the retention of the pattern of the disappearing material and the repellent layer.

  The formation thickness of the repellent layer is a range that does not affect the disappearance treatment (dissolution treatment) of the disappearing material, and preferably depends on the pattern width and thickness (height) of the disappearing material and the coating thickness of the ceramic slurry. Is about several μm to several tens of μm.

  Embodiments of the present invention will be specifically described below with reference to the drawings. FIG. 1 to FIG. 3 are flowcharts showing the main steps in the method for producing a ceramic green sheet of the present invention. 1 to 3 all show cross sections of the main parts such as a base material and a sheet. Further, a configuration that exhibits the same effect as the configuration shown in FIG. 1 will be described using the same reference numerals in FIGS. 2 and 3. Further, those skilled in the art will easily understand that the sheets shown in FIGS. 1 to 3 are different from the actually produced scales.

  Further, in the following examples, only preferred embodiments of the present invention are illustrated, and various types of ceramic green sheets are prepared in the same manner as in the examples, depending on the target multilayer electronic component. Those skilled in the art will readily understand that they can be fabricated and manufactured.

  If a positive photoresist is used as the disappearing material, the light transmittance of the repelling layer is not considered by performing an exposure treatment after forming the pattern with the disappearing material and before forming the repelling layer. May be. Conversely, if the repellent layer is light-transmitting and the disappearing material has a thickness and pattern that can be sufficiently exposed, the exposure treatment should be performed after the repellent layer is formed or after the alkali-insoluble insulating layer (ceramic layer) is formed. (Not shown).

  As shown in FIG. 1, a positive-type disappearing material layer 2 that can be dissolved in a solvent is formed on a substrate 1 that has been subjected to a mold release treatment. The member having the disappearing material layer 2 is exposed using a photomask 3 and developed to form a positive-type disappearing material as a pattern 4. The entire surface of the member on which this pattern 4 is formed is exposed from the upper side, or when the base material 1 subjected to the mold release treatment is light transmissive, it is exposed from the base material side or from both sides, and the pattern 4 Irradiate with light.

  A ceramic slurry repellent layer 5 is formed on the pattern 4 by an arbitrary method such as a printing method.

  An insulating layer 6 made of an alkali solvent insoluble insulating material is formed on the member having the ceramic slurry repellent layer 5 on the pattern 4. At this time, as shown in FIG. 1, the insulating layer 6 has substantially the same thickness as the total thickness of the pattern 4 and the ceramic slurry repellent layer 5 or the total thickness of the pattern 4 and the ceramic slurry repellent layer 5. The thickness may be formed so as to be substantially the same as the pattern 4 or the like.

  Next, the member on which the insulating layer 6 is formed is subjected to a dissolution treatment with an alkaline solvent to remove the pattern portion, thereby forming a through hole (extracted pattern) 7.

  Using the obtained ceramic green sheet having the through hole 7, an electrode or the like is arbitrarily incorporated, and a plurality of ceramic green sheets are laminated, pressed and fired to produce a desired multilayer electronic component.

  As shown in FIG. 2, an alkali low-solubility insulating layer is formed as a disappearing material adhesion layer 8 with a low-solubility insulating material in a solvent on the base material 1 subjected to the mold release treatment. On the member having the disappearing material adhesion layer 8, the positive disappearing material layer 2 that is soluble in the solvent is formed. The member having the disappearing material layer 2 is exposed using a photomask 3 and developed to form a positive type material as a pattern 4. In this exposure and development process, the disappearing material adhesion layer 8 other than the peripheral portion of the pattern 4 may be removed. The entire surface of the member on which this pattern 4 is formed is exposed from the upper side, or when the base material 1 subjected to the mold release treatment is light transmissive, it is exposed from the base material side or from both sides, and the pattern 4 Irradiate with light.

  A ceramic slurry repellent layer 5 is formed on the pattern 4 by an arbitrary method such as a printing method.

  An insulating layer 6 made of an alkali solvent insoluble insulating material is formed on the member having the ceramic slurry repellent layer 5 on the pattern 4. At this time, as shown in FIG. 2, the insulating layer 6 has substantially the same thickness as the sum of the pattern 4 and the ceramic slurry repellent layer 5 or the sum of the pattern 4 and the ceramic slurry repellent layer 5. The thickness may be formed so as to be substantially the same as the pattern 4 or the like.

  Next, the member in which the insulating layer 6 is formed is subjected to a dissolution treatment with an alkaline solvent to remove the pattern portion made of the positive type disappearance material and the disappearance material adhesion layer 8 under the pattern portion, A through hole (extracted pattern) 7 is formed.

  Using the ceramic green sheet having the through-hole 7, an electrode or the like is arbitrarily incorporated, and a plurality of ceramic green sheets are laminated, pressed, and fired to produce a desired multilayer electronic component.

  In this embodiment, the case where the disappearing material adhesion layer is made of an insulating material having a low alkali solubility is shown, but the disappearing material can be used before and after firing or within a range that does not affect the characteristics.

  As shown in FIG. 3, an alkali-soluble vanishing material layer is formed as a vanishing material adhesion layer 9 on a base material 1 that has been subjected to a mold release treatment using a vanishing material that is soluble in a solvent. On the member having the disappearing material adhesion layer 9, the positive-type disappearing material layer 2 that can be dissolved in a solvent is formed. The member having the disappearing material layer 2 is exposed using a photomask 3 and developed to form a pattern made of the disappearing material adhesion layer and the positive disappearing material on the substrate. The entire surface of the patterned member is exposed from the upper side, or when the base material 1 subjected to the release treatment is light transmissive, it is exposed from the base material side or from both sides, and light is applied to the pattern 10. Irradiate.

  The ceramic slurry repellent layer 5 is formed on the pattern 10 by an arbitrary method such as a printing method.

  An insulating layer 6 made of an alkali solvent insoluble insulating material is formed on a member having the ceramic slurry repellent layer 5 on this pattern. At this time, as shown in FIG. 3, the insulating layer 6 has substantially the same thickness as the sum of the pattern 10 and the ceramic slurry repellent layer 5 or the sum of the pattern 10 and the ceramic slurry repellent layer 5. It is good also as forming so that it may become thickness or the thickness substantially the same as the pattern 10.

  Next, the member on which the insulating layer 6 is formed is subjected to a dissolution treatment with an alkaline solvent to remove the pattern portion, thereby forming a through hole (extracted pattern) 7.

  Using the ceramic green sheet having the through-hole 7, an electrode or the like is arbitrarily incorporated, and a plurality of ceramic green sheets are laminated, pressed, and fired to produce a desired multilayer electronic component.

  In this embodiment, the case where the disappearing material adhesion layer is made of an alkali-soluble disappearing material is shown, but an insulating material can also be used before and after firing or within a range that does not affect the characteristics.

  The method for producing a ceramic green sheet according to the present invention does not use a photosensitive slurry, has a good production cost, has a simple process, has no restrictions on the materials used, and produces a wide variety of multilayer electronic components. Can be suitably used.

It is a flowchart which shows an example of the processing method of the ceramic green sheet of this invention. It is a flowchart which shows another example of the processing method of the ceramic green sheet of this invention. It is a flowchart which shows another example of the processing method of the ceramic green sheet of this invention.

Explanation of symbols

1: Substrate 2: Alkali-soluble disappearing material 3: Photomask 4: Pattern 5: Ceramic slurry repellent layer 6: Alkali insoluble insulating layer 7: Through hole (extracted pattern)
8: Alkali low solubility disappearance material adhesion layer 9: Alkali soluble disappearance material adhesion layer 10: Pattern

Claims (8)

A method for producing a ceramic green sheet for a multilayer electronic component in which an insulating material is formed after forming a pattern with a disappearing material on a substrate, and a pattern groove or a through hole is formed by a disappearing process,
at least,
Forming a pattern of a disappearing material on a substrate;
Forming a ceramic slurry repellent layer on the pattern of the disappearing material;
A step of forming an insulator material on a member having a pattern of a disappearing material in which the ceramic slurry is repelled;
A step of performing disappearance treatment on the member on which the insulator material is formed,
And a method for producing a ceramic green sheet. A method for producing a ceramic green sheet for a multilayer electronic component in which an insulating material is formed after forming a pattern with a disappearing material on a substrate, and a pattern groove or a through hole is formed by a disappearing process,
at least,
Forming a lost material adhesion layer on the substrate;
Forming a pattern of the disappearing material on the member on which the disappearing material adhesion layer is formed,
Forming a ceramic slurry repellent layer on the pattern of the disappearing material;
A step of forming an insulator material on a member having a pattern of a disappearing material in which the ceramic slurry is repelled;
A step of performing disappearance treatment on the member on which the insulator material is formed,
And a method for producing a ceramic green sheet. The disappearing material is made of a photosensitive material,
3. The vanishing material pattern is formed by photolithography after forming the vanishing material on the substrate or the vanishing material adhesion layer. 4. Manufacturing method of ceramic green sheet. For the height of the pattern due to the disappearing material,
4. The method of manufacturing a ceramic green sheet according to claim 1, wherein the thicknesses of the insulator material layers are formed substantially coincident with each other. 5.   5. The production of a ceramic green sheet according to claim 1, wherein the step of performing the disappearance treatment forms a penetration pattern in accordance with the disappearance material pattern by a dissolution treatment. Method.   The method for producing a ceramic green sheet according to claim 2, wherein the disappearing material adhesion layer is made of an insulator material.   The method for producing a ceramic green sheet according to claim 2, wherein the disappearing material adhesion layer is made of an alkali-soluble material. A ceramic green sheet group including a ceramic green sheet obtained by the method for producing a ceramic green sheet according to any one of claims 1, 2, 3, 4, 5, 6 or 7, is laminated, pressed, A multilayer ceramic electronic component formed by firing.

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