WO2024004461A1 - 導電パターン付きセラミックグリーンシートの製造方法 - Google Patents

導電パターン付きセラミックグリーンシートの製造方法 Download PDF

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Publication number
WO2024004461A1
WO2024004461A1 PCT/JP2023/019487 JP2023019487W WO2024004461A1 WO 2024004461 A1 WO2024004461 A1 WO 2024004461A1 JP 2023019487 W JP2023019487 W JP 2023019487W WO 2024004461 A1 WO2024004461 A1 WO 2024004461A1
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Prior art keywords
ceramic green
green sheet
photosensitive layer
conductive pattern
conductive
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English (en)
French (fr)
Japanese (ja)
Inventor
大輔 松下
大樹 橋本
皓平 高瀬
麻里恵 小山
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Toray Industries Inc
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Toray Industries Inc
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Priority to JP2023532473A priority Critical patent/JPWO2024004461A1/ja
Priority to CN202380033941.2A priority patent/CN119013624A/zh
Publication of WO2024004461A1 publication Critical patent/WO2024004461A1/ja
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables

Definitions

  • An inductor which is a type of electronic component, has a coil-shaped internal electrode inside an insulator made of ceramic, and generally the internal electrode is formed in the form of a wire wound on a flat insulating layer made of ceramic. is formed by laminating multiple layers.
  • a photosensitive paste (for example, see Patent Document 1) has been proposed that contains an alkali-soluble resin having an acid value of 200 to 300 mgKOH/g, a reactive compound, and a photoreaction initiator.
  • Inductor manufacturing methods include, for example, forming internal electrodes on ceramic green sheets and stacking them in multiple layers, and forming internal electrodes and ceramic green sheets alternately and repeatedly on ceramic green sheets. Can be mentioned. The inventors have found that in these methods, when a photosensitive paste as described in Patent Document 1 is applied directly onto a ceramic green sheet to form a pattern, the line width at the bottom of the internal electrodes of each layer becomes narrower. It was found that there was a problem in that it was difficult to form high-definition internal wiring. This is because when a photosensitive paste coating film is formed on a ceramic green sheet, the solvent contained in the photosensitive paste dissolves the organic components contained in the ceramic green sheet, and the dissolved organic components are mixed into the photosensitive conductive paste.
  • an object of the present invention is to provide a method for manufacturing a ceramic green sheet with a conductive pattern having a high-definition conductive pattern that suppresses the occurrence of wire breakage.
  • the present invention mainly has the following configuration.
  • (1) Containing conductive particles (a), non-conductive particles (b), alkali-soluble resin (c), photosensitizer (d) and solvent (e) on a base material, and the content of solvent (e) is preparing a substrate with a photosensitive layer having a photosensitive layer of 5.0% by mass or less, and transferring the photosensitive layer from the substrate onto a ceramic green sheet (transfer step); A step of bringing an exposure mask into contact with the photosensitive layer and exposing it to light (exposure step A), and Step of developing the photosensitive layer after exposure to form a conductive pattern (development step)
  • a ceramic green sheet with a conductive pattern that suppresses the occurrence of wire breakage and has a high-definition conductive pattern it is possible to obtain a ceramic green sheet with a conductive pattern that suppresses the occurrence of wire breakage and has a high-definition conductive pattern.
  • FIG. 2 is a schematic diagram of a mask pattern of an exposure mask used in Examples.
  • the ceramic green sheet with a conductive pattern in the present invention has a ceramic green sheet and a conductive pattern on a base material.
  • the ceramic green sheet when used in an inductor, by laminating a plurality of layers and firing them, the ceramic green sheet forms an insulating layer and the conductive pattern forms an internal electrode.
  • the method for manufacturing a ceramic green sheet with a conductive pattern of the present invention includes a transfer step or a lamination step, an exposure step, and a development step, which will be described later, in this order.
  • the method is characterized in that a photosensitive layer containing a predetermined amount of solvent is laminated onto the ceramic green sheet through a transfer process or a lamination process. This suppresses the stickiness of the photosensitive layer and thinning of the bottom of the conductive pattern caused by the solvent (e), making it possible to form a high-definition pattern and suppressing wire breakage.
  • high-temperature drying on the ceramic green sheet is not required, shrinkage of the ceramic green sheet due to heat can be suppressed and a high-definition pattern can be formed.
  • the first aspect of the method for manufacturing a ceramic green sheet with a conductive pattern of the present invention is as follows: On the base material, conductive particles (a), non-conductive particles (b), alkali-soluble resin (c), photosensitizer (d) and solvent (e) are contained, and the content of solvent (e) is 5.0.
  • a step of bringing an exposure mask into contact with the photosensitive layer and exposing it to light exposure step A
  • Step of developing the photosensitive layer after exposure to form a conductive pattern development step
  • the transfer step since the photosensitive layer is transferred onto the ceramic green sheet, the photosensitive layer is exposed on the surface, and in the exposure step A, contact exposure in which the photosensitive layer and the exposure mask are brought into contact is possible. Therefore, a pattern with higher definition can be formed.
  • a second aspect of the method for manufacturing a ceramic green sheet with a conductive pattern of the present invention is On the base material, conductive particles (a), non-conductive particles (b), alkali-soluble resin (c), photosensitizer (d) and solvent (e) are contained, and the content of solvent (e) is 5.0.
  • a process of preparing a base material with a photosensitive layer having a photosensitive layer of less than % by mass, and laminating the base material with a photosensitive layer on the ceramic green sheet so that the photosensitive layer is in contact with the ceramic green sheet (lamination process) , A step of bringing an exposure mask into contact with the base material of the photosensitive layer-attached base material to expose it to light (exposure step B), and Step of developing the photosensitive layer after exposure to form a conductive pattern (development step) in this order.
  • exposure step B Step of developing the photosensitive layer after exposure to form a conductive pattern in this order.
  • the lamination process since the base material with a photosensitive layer is laminated on the ceramic green sheet, the base material is present on the photosensitive layer, and in the exposure process B, the photosensitive layer is exposed through the base material. Since the photosensitive layer is protected by the base material, disconnection of the conductive pattern can be further suppressed.
  • the base material with a photosensitive layer used in the present invention includes, for example, conductive particles (a), non-conductive particles (b), alkali-soluble resin (c), photosensitizer (d), and solvent (e) on the base material. It can be obtained by applying a photosensitive paste containing the above by screen printing method and drying to form a photosensitive layer.
  • Base Material examples include metal substrates, glass substrates, and plastic films.
  • PET polyethylene terephthalate
  • cycloolefin polymer polycarbonate
  • polyimide polyimide
  • aramid plastic films containing resins such as fluororesins, acrylic resins, and polyurethane resins are preferred, and films containing PET, cycloolefin polymers, and polycarbonates are more preferred.
  • one or both sides of the plastic film be subjected to a mold release treatment using a silicone resin, a fluororesin, or the like.
  • the thickness of the base material is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more.
  • the thickness is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 75 ⁇ m or less.
  • the conductive particles (a) in the present invention refer to particles having a specific resistance of 1.0 ⁇ 10 ⁇ 4 ⁇ m or less at 20° C., and have the function of imparting conductivity to a conductive pattern by firing.
  • Examples of the conductive particles (a) include metals such as silver, gold, copper, platinum, palladium, tin, nickel, aluminum, tungsten, molybdenum, ruthenium, chromium, titanium, and indium, alloys thereof, carbon, and titanium nitride. Examples include particles such as. Two or more types of these may be contained. Among these, silver, copper, and gold particles are preferred from the viewpoint of conductivity, and silver particles are more preferred from the viewpoint of stability.
  • Non-conductive particles (b) refer to insulating particles having a specific resistance of more than 1.0 ⁇ 10 ⁇ 4 ⁇ m at 20° C., and have the effect of suppressing shrinkage of the conductive pattern during firing.
  • non-conductive particles (b) examples include alumina (Al 2 O 3 ), zirconia (ZrO 2 ), magnesia (MgO), beryllia (BeO), mullite (3Al 2 O 3 .2SiO 2 ), and cordierite ( 5SiO2.2Al2O3.2MgO ), spinel ( MgO.Al2O3 ), forsterite ( 2MgO.SiO2 ) , anorthite ( CaO.Al2O3.2SiO2 ) , celsian ( BaO.Al2 ) O 3.2SiO 2 ), silica (SiO 2 ), barium titanate (BaTiO 3 , aluminum nitride (AlN), ferrite (garnet type: Y 3 Fe5O 12 system, spinel type: MeFe 2 O 4 system), “SiO 2 , Al 2 O 3 , CaO, B 2 O 3 , MgO, TiO 2 ,
  • glass particles that further suppress firing defects are mentioned. From this point of view, particles of titania, alumina, silica, cordierite, mullite, spinel, barium titanate, and zirconia are preferred, and silica particles are more preferred.
  • the D50 of the non-conductive particles (b) is preferably 5 ⁇ m or less, more preferably 0.1 ⁇ m or less, and even more preferably 0.05 ⁇ m or less, from the viewpoint of suppressing shrinkage of the conductive pattern during firing.
  • the non-conductive particles (b) are added to water, subjected to ultrasonic treatment for 300 seconds, and then treated using Nanotrac Wave II-UZ251 (manufactured by Microtrac BEL). It can be determined by dynamic light scattering method.
  • the content of the non-conductive particles (b) in the photosensitive paste is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and 0.1% by mass or more, more preferably 0.2% by mass or more, from the viewpoint of suppressing shrinkage of the conductive pattern during firing. More preferably, the content is 4% by mass or more. On the other hand, from the viewpoint of electrical conductivity, the content of the non-conductive particles (b) is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less.
  • Alkali-soluble resin (c) refers to a resin having a carboxyl group and/or a hydroxyl group in its side chain, and serves as a binder resin for a photosensitive paste, and also has the function of forming a pattern by being dissolved during development.
  • the alkali-soluble resin (c) is preferably an acrylic resin, and preferably a copolymer of an acrylic monomer having a carbon-carbon double bond and another monomer.
  • acrylic monomer and other monomers having a carbon-carbon double bond include those exemplified as raw materials for the acrylic resin, which is an example of the alkali-soluble resin (b-1), in JP 2019-215446A. Can be mentioned.
  • the alkali-soluble resin (c) preferably has a carbon-carbon double bond in the side chain and/or at the end of the molecule, which can improve the curing reaction rate during exposure.
  • Examples of the structure having a carbon-carbon double bond include a vinyl group, an allyl group, an acrylic group, and a methacryl group. You may have two or more types of these.
  • a method for introducing a carbon-carbon double bond into the alkali-soluble resin (c) for example, in the case of an acrylic resin, a glycidyl group or an isocyanate group is added to a mercapto group, an amino group, a hydroxyl group, or a carboxyl group in the acrylic resin. Examples include a method of reacting a group with a compound having a carbon-carbon double bond, acrylic acid chloride, methacrylic acid chloride, allyl chloride, and the like.
  • Examples of compounds having a glycidyl group and a carbon-carbon double bond include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonate, glycidyl isocrotonate, "cyclomer ( (registered trademark)" M100, A200 (manufactured by Daicel Chemical Industries, Ltd.), and the like.
  • Examples of the compound having an isocyanate group and a carbon-carbon double bond include acryloyl isocyanate, methacryloyl isocyanate, acryloyl ethyl isocyanate, and methacryloyl ethyl isocyanate. Two or more types of these may be used.
  • the alkali-soluble resin (c) contains a carboxyl group-containing resin that does not have an unsaturated double bond.
  • carboxyl group-containing resins that do not have unsaturated double bonds include solid JONCRYL67 (glass transition temperature 73°C), JONCRYL678 (glass transition temperature 85°C), and JONCRYL611 (glass transition temperature) manufactured by BASF Japan Co., Ltd.
  • JONCRYL693 glass transition temperature 84°C
  • JONCRYL682 glass transition temperature 56°C
  • JONCRYL690 glass transition temperature 102°C
  • JONCRYL819 glass transition temperature 57°C
  • JONCRYLJDX-C3000A glass transition temperature 65°C
  • JONCRYLJDX-C3080 glass transition temperature 134°C
  • JONCRYL52J dissolved in alkaline water glass transition temperature 56°C
  • JONCRYLPDX-6157 glass transition temperature 84°C
  • JONCRYL60J glass transition temperature 85°C
  • JONCRYL63J glass transition temperature 73°C
  • JONCRYL70J glass transition temperature 102°C
  • JONCRYLJDX-6180 glass transition temperature 134°C
  • JONCRYLHPD-196 glass transition temperature 85°C
  • JONCRYLHPD-96J glass transition temperature 102°C
  • the glass transition temperature of the carboxyl group-containing resin having no unsaturated double bonds is preferably 110°C or lower, more preferably 30°C to 70°C.
  • the content of the alkali-soluble resin (c) in the photosensitive paste is preferably 1 to 10% by mass from the viewpoint of photolithography processability, viscosity characteristics, etc.
  • Photosensitizer (d) examples include photopolymerization initiators and dissolution inhibitors. From the viewpoint of forming a thicker conductive pattern, a photopolymerization initiator is preferable.
  • the photopolymerization initiator absorbs short wavelength light such as ultraviolet rays and decomposes, or generates radicals through a hydrogen abstraction reaction, thereby imparting photocurability and enabling pattern formation using negative photolithography.
  • Examples of the photopolymerization initiator include those exemplified as the photoreaction initiator (d) in JP-A-2019-215446. From the viewpoint of photocurability, oxime-based photopolymerization initiators are preferred.
  • the dissolution inhibitor increases the solubility of the exposed area in the developer and enables pattern formation by positive photolithography.
  • the dissolution inhibitor is preferably one that generates an acid when exposed to the exposure energy used in the exposure step described below.
  • Examples include diazodisulfone compounds, triphenylsulfonium compounds, and quinonediazide compounds.
  • Examples of the diazodisulfone compound include bis(cyclohexylsulfonyl)diazomethane, bis(tertiarybutylsulfonyl)diazomethane, and bis(4-methylphenylsulfonyl)diazomethane.
  • triphenylsulfonium compounds include diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate, diphenyl(4-methoxy
  • examples include phenyl)sulfonium trifluoromethanesulfonate.
  • Examples of quinonediazide compounds include those in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy compound through an ester bond, those in which the sulfonic acid of quinonediazide is bonded to a polyamino compound through a sulfonamide bond, and those in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy polyamino compound through an ester bond and/or or those with sulfonamide bonds. Two or more types of these may be contained.
  • the content of the photosensitizer (d) in the photosensitive paste is preferably 0.1 to 2% by mass.
  • the solvent (e) has the effect of adjusting the viscosity of the photosensitive paste.
  • the boiling point of the solvent (e) under atmospheric pressure is 150°C or higher from the viewpoint of improving the applicability when continuously applying the photosensitive paste, improving the peelability from the substrate, and improving the transferability. is preferred.
  • the boiling point of the solvent (e) under atmospheric pressure is preferably 300° C. or lower from the viewpoint of dry removability.
  • solvents having a boiling point within the above range include ethylene glycol hexyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol n-butyl ether, diethylene glycol ethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol methyl ether, diethylene glycol monoethyl ether, Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol n-butyl ether, dipropylene glycol propyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether, dipropylene glycol methyl ether acetate, Propylene glycol monomethyl ether acetate, dimethyl imidazolidinone, dimethyl sulfoxide, triethylene glycol dimethyl ether, propylene glyco
  • the content of the solvent (e) in the photosensitive paste is preferably 5 to 40% by mass from the viewpoint of paste viscosity.
  • the photosensitive paste in the present invention contains a leveling agent. Containing a leveling agent has the effect of suppressing repellency when applying the photosensitive paste onto a substrate and improving the releasability of the photosensitive layer.
  • Leveling agents include, for example, anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate, lauryl trimethylammonium chloride, lauryl dimethylamine oxide, and lauryl carboxylic acid.
  • Main skeletons include amphoteric surfactants such as methylhydroxyethylimidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate, polydimethylsiloxane, and polymethylalkylsiloxane.
  • silicone surfactants examples include silicone surfactants, fluorine surfactants, and acrylic surfactants.
  • the polymethylalkylsiloxane may be an aralkyl-modified polymethylalkylsiloxane.
  • silicone surfactants having a main skeleton such as polydimethylsiloxane or acrylic surfactants are preferred.
  • the photosensitive layer in the present invention contains polyether-modified polydimethylsiloxane as a silicone surfactant having a main skeleton such as polydimethylsiloxane.
  • the photosensitive paste in the present invention contains a photopolymerizable compound having an unsaturated bond, a plasticizer, a leveling agent, a dispersant, a surfactant, a silane coupling agent, an antifoaming agent, as long as the desired properties thereof are not impaired. It may also contain additives such as pigments and dyes.
  • the photosensitive paste in the present invention can be obtained, for example, by dissolving and/or dispersing the above-mentioned components (a) to (d) and optionally other additives in a solvent (e).
  • examples of devices for dissolving and/or dispersing include dispersing machines such as three rollers and ball mills, and kneading machines.
  • the dissolution and/or dispersion may be carried out at room temperature or by heating.
  • a photosensitive paste is applied onto the substrate and dried to form a photosensitive layer.
  • Examples of the coating method include a spray coating method, a roll coating method, a screen printing method, a coating method using a blade coater, a die coater, a calendar coater, a meniscus coater, a bar coater, and the like.
  • the screen printing method is preferred from the viewpoints of suitability for thick film coating and continuous productivity.
  • drying method examples include heating drying using a heating device such as an oven, a hot plate, and infrared rays, and vacuum drying.
  • the heating temperature is preferably 40 to 100°C, and conditions such as the heating device, drying temperature, and drying time are preferably selected so that the solvent (e) in the photosensitive layer is 5.0% by mass or less.
  • the content of the solvent (e) in the photosensitive layer is preferably 5.0% by mass or less.
  • the content of the solvent (e) exceeds 5.0% by mass, it may become difficult to form a high-definition pattern due to the adhesiveness of the photosensitive layer and the thinning of the bottom of the conductive pattern. Additionally, wire breakage may occur more easily.
  • the content of the solvent (e) is preferably 2.0% by mass or less, and can further improve line width uniformity.
  • the content of the solvent (e) in the photosensitive layer is preferably 0.10% by mass or more, and can improve peelability from the base material and improve transferability.
  • the thickness of the photosensitive layer in the substrate with a photosensitive layer is preferably greater than 10 ⁇ m, and disconnection of the conductive pattern can be suppressed.
  • the thickness of the photosensitive layer is preferably 25 ⁇ m or less, and since exposure light can easily reach the deep part of the photosensitive layer in the exposure step described below, a more precise pattern can be formed.
  • the above-described base material with a photosensitive layer is prepared, and the photosensitive layer is transferred from the base material onto a ceramic green sheet.
  • the photosensitive layer may be peeled off from the base material and laminated on the ceramic green sheet, or the base material with the photosensitive layer is laminated on the ceramic green sheet so that the photosensitive layer is in contact with the ceramic green sheet, and then the base material is laminated on the ceramic green sheet.
  • the material may be peeled off.
  • it is preferable to transfer by pressure bonding and examples of the transfer device include a press, a roll laminator, and the like.
  • the transfer temperature is preferably 20°C to 200°C.
  • the transfer pressure is preferably 0.1 MPa to 2.0 MPa.
  • the pressurization time is preferably 10 to 300 seconds. Examples of the atmosphere include air, nitrogen, and vacuum.
  • the ceramic green sheet examples include sheets of insulating compositions containing glass, ceramic, inorganic powder such as glass ceramic, and binder resin. It is also preferable that the ceramic green sheet contains a photosensitive organic component, so that it can be imparted with photosensitivity. In this case, the insulating composition preferably contains a photosensitive organic component. Further, a sheet of the insulating composition may be provided on a substrate such as a plastic film or an optical resin plate, which are exemplified as the base material of the base material with a photosensitive layer.
  • Ceramic green sheets can be obtained, for example, by applying an insulating composition prepared by dispersing the above-mentioned inorganic powder in a binder resin into a paste onto a substrate such as a plastic film or an optical resin plate.
  • the coating method include the methods exemplified above as the photosensitive paste coating method. If the ceramic green sheet is photosensitive, the pattern may be formed by photolithography.
  • the photosensitive organic component examples include the alkali-soluble resin (c), the photosensitizer (d), and the photopolymerizable compound having an unsaturated bond, which were exemplified as the raw material for the conductive paste described above.
  • the photosensitive layer is exposed to light by bringing it into contact with an exposure mask.
  • an exposure mask By eliminating the gap between the exposure mask and the photosensitive layer, it is possible to suppress the spread of the exposure light due to diffraction and the line thickening caused by the reflection of the exposure light between the surface layer of the photosensitive layer and the exposure mask, making it possible to form higher-definition patterns. can. Further, the pattern line width uniformity is improved.
  • Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, the i-line (wavelength: 365 nm), h-line (wavelength: 405 nm), and g-line (wavelength: 436 nm) of a mercury lamp are preferred.
  • the exposed photosensitive layer is developed to form a conductive pattern.
  • an alkaline developer is preferable, and examples thereof include those exemplified as a developer when performing alkaline development in JP-A-2019-215446.
  • a developing method for example, a method in which a ceramic green sheet having a photosensitive layer after exposure is left still, a method in which a developer is sprayed while being transported or rotated, a method in which a ceramic green sheet having a photosensitive layer after exposure is placed in a developer solution, Examples include a method of immersion, and a method of applying ultrasonic waves while immersing a ceramic green sheet having a photosensitive layer after exposure in a developer.
  • the pattern obtained by development may be subjected to rinsing treatment using a rinsing liquid.
  • a rinsing liquid examples include those exemplified as the rinsing liquid in JP-A No. 2019-215446.
  • drying step a step of drying the remaining solvent and developer in the photosensitive layer.
  • drying step By drying and removing the residual solvent and developer, the shrinkage rate can be reduced when producing the fired body described below.
  • drying method include the methods exemplified as the drying method for forming the photosensitive layer.
  • Exposure process B An exposure mask is brought into contact with the base material of the base material with a photosensitive layer, and the base material is exposed to light.
  • the gap between the exposure mask and the photosensitive layer can be kept constant, improving the uniformity of the pattern line width. Furthermore, since the exposure mask and the photosensitive layer do not come into direct contact with each other, it is possible to suppress defects in the photosensitive layer and further suppress disconnections in the conductive pattern. Except for peeling off the base material after exposure, the rest is the same as (exposure step A) in the first embodiment.
  • (Developing step) and (laminating step) are the same as in the first embodiment, and may further include a drying step.
  • the ceramic green sheets with conductive patterns in the present invention can be used as a laminate by laminating a plurality of them. By stacking, the thickness of the conductive pattern can be increased.
  • the number of laminated layers is preferably 2 to 30 layers. By setting the number of laminated layers to 30 or less, the influence of misalignment between layers can be suppressed.
  • the first aspect of the method for manufacturing a laminate of the present invention is: forming a first conductive pattern by the method described above to obtain a ceramic green sheet with a conductive pattern; forming a ceramic green sheet on the conductive pattern side of the first conductive patterned ceramic green sheet, and It is preferable to have a step of forming a second conductive pattern by the method described above on the ceramic green sheet formed with the first conductive pattern.
  • the second aspect of the method for manufacturing a laminate of the present invention is Obtaining a plurality of ceramic green sheets with conductive patterns by the method described above, and It is preferable to include a step of laminating and thermocompression bonding a plurality of ceramic green sheets with conductive patterns.
  • the lamination method include a method of stacking ceramic green sheets using guide holes.
  • the thermocompression bonding device include a hydraulic press machine. The thermocompression temperature is preferably 90 to 130°C, and the thermocompression pressure is preferably 5 to 20 MPa.
  • the ceramic green sheet or laminate with a conductive pattern in the present invention can be fired and used as a fired product.
  • the thickness of the fired body is preferably 2 ⁇ m or more from the viewpoint of suppressing wire breakage during firing. On the other hand, the thickness of the fired body is preferably 20 ⁇ m from the viewpoint of suppressing swelling during firing.
  • the line width of the conductive pattern in the fired body is preferably 5 ⁇ m or more from the viewpoint of suppressing disconnection during firing. On the other hand, the line width of the conductive pattern in the fired body is preferably 40 ⁇ m or less from the viewpoint of improving the aspect ratio.
  • the method for producing a fired body of the present invention includes: It is preferable to have a step of obtaining a ceramic green sheet with a conductive pattern or a laminate thereof by the above-described manufacturing method, and a step of firing the obtained ceramic green sheet with a conductive pattern or a laminate thereof.
  • the firing method include a method in which heat treatment is performed at 300 to 600°C for 5 minutes to several hours, and then further heat treatment is performed at 850 to 900°C for 5 minutes to several hours.
  • a first conductive pattern is formed by the method for manufacturing a ceramic green sheet with a conductive pattern of the present invention, and a ceramic green sheet with a conductive pattern is obtained.
  • a ceramic green sheet is formed on the conductive pattern side of the first ceramic green sheet with a conductive pattern.
  • a via hole is formed in the formed ceramic green sheet, and a conductor is embedded in the via hole to form an interlayer connection wiring.
  • the via hole forming method include laser irradiation.
  • vias can be formed with high precision by exposing and developing the sheet through a mask having a via shape.
  • Examples of the method for forming the interlayer connection wiring include a method of embedding conductive paste using a screen printing method and drying it.
  • Examples of the conductive paste include pastes containing copper, silver, and silver-palladium alloys. Subsequently, a second conductive pattern is formed on the ceramic green sheet with a conductive pattern formed thereon by the manufacturing method of the present invention. By repeating these steps, a laminate can be obtained. Further, a laminate can also be obtained by preparing a plurality of ceramic green sheets with conductive patterns according to the present invention, stacking them and thermocompression bonding them.
  • a multilayer chip inductor can be obtained by dicing the obtained multilayer body into a desired chip size, firing it, applying terminal electrodes, and plating it. Examples of these methods include the method exemplified as a method for manufacturing a multilayer chip inductor in JP-A-2019-215446.
  • Conductive particles (a) Ag particles (hereinafter referred to as Ag particles) having a particle size (D50) of 2.1 ⁇ m and a specific resistance of 1.6 ⁇ 10 ⁇ 8 ⁇ m.
  • the particle size (D50) of the conductive particles was measured by a laser light scattering method using a particle size distribution measuring device (Microtrac HRA Model No. 9320-X100; manufactured by Nikkiso Co., Ltd.).
  • Non-conductive particles (b) Particle size (D50) 12 nm, insulating silica powder "AEROSIL (registered trademark)" R972 (manufactured by Nippon Aerosil Co., Ltd.) (hereinafter referred to as Aerosil R972).
  • the particle size (D50) of the non-conductive particles was determined by adding the non-conductive particles to water, performing ultrasonic treatment for 300 seconds, and then using a dynamic light scattering method using Nanotrac Wave II-UZ251 (manufactured by Microtrac BEL). It was measured.
  • Alkali-soluble resin (c): c-1: Carboxyl groups are added by adding 40 moles of glycidyl methacrylate to 100 moles of carboxyl groups of a copolymer of methacrylic acid/methyl methacrylate/styrene 54/23/23 (mole ratio). A containing acrylic copolymer (c-1) was obtained. (Contains unsaturated double bonds, weight average molecular weight 30,000, glass transition temperature 110°C).
  • c-2 JONCRYL690 (no unsaturated double bonds, polymerization average molecular weight 16,500, glass transition temperature 102°C; manufactured by BASF Japan Co., Ltd.).
  • JONCRYL819 no unsaturated double bonds, polymerization average molecular weight 14,500, glass transition temperature 57°C; manufactured by BASF Japan Co., Ltd.).
  • e-2 Propylene glycol monomethyl ether acetate (boiling point at atmospheric pressure: 146°C).
  • Photosensitive monomer ester structure-containing urethane acrylate NK oligo UA-122P (viscosity 7.0 Pa ⁇ s, weight average molecular weight 1,100, manufactured by Shin Nakamura Chemical Co., Ltd.) (hereinafter referred to as UA-122P).
  • Leveling agent “Disparon (registered trademark)” L-1980N (manufactured by Kusumoto Kasei Co., Ltd.) (hereinafter referred to as L-1980N).
  • G-700 Floren G-700 (manufactured by Kyoeisha Chemical Co., Ltd.) (hereinafter referred to as G-700).
  • the obtained composition was applied onto a PET film with a thickness of 100 ⁇ m and dried to produce a substrate with a ceramic green sheet.
  • ⁇ Thickness of photosensitive layer> The thickness of the photosensitive layer prepared in each Example and Comparative Example was measured using a stylus-type step meter ("Surfcom (registered trademark)"1400; manufactured by Tokyo Seimitsu Co., Ltd.).
  • thermocompression temperature was 50 to 130°C
  • thermocompression pressure was 0.1 to 0.3MPa
  • thermocompression time was 30s (fixed), from low temperature and low pressure conditions.
  • a conductive pattern corresponding to an exposure mask opening width of 15 ⁇ m was cut in the line width direction, and a cross section of the pattern was examined using a scanning electron microscope (S2400). (manufactured by Hitachi, Ltd.) at a magnification of 3,000 times, the top width and bottom width of the conductive pattern were measured, and the difference between the top width and the bottom width was calculated.
  • S2400 scanning electron microscope
  • Example 1 ⁇ Preparation of photosensitive paste>
  • 14.8g c-1, 2.0g N-1919, 60.0g e-1, 7.5g UA-122P, 0.4g L-1980N, 0.4g G -700 and mixed using a rotation-revolution vacuum mixer "Awatori Rentaro (registered trademark)" ARE-310 (manufactured by Shinky Co., Ltd.) to obtain 85.1 g of a resin solution.
  • the obtained resin solution, 248.1 g of Ag particles, and 1.6 g of Aerosil R972 were mixed and kneaded using three rollers (EXAKT M-50; manufactured by EXAKT) to form 334.8 g of photosensitive material.
  • Got the paste In a 200mL clean bottle, 14.8g c-1, 2.0g N-1919, 60.0g e-1, 7.5g UA-122P, 0.4g L-1980N, 0.4g G -700 and mixed using a rotation-revolution vacuum mixer "Awatori Rentar
  • the photosensitive paste obtained by the above method was applied by screen printing onto a PET substrate with a thickness of 50 ⁇ m, and dried at a temperature of 55° C. for 15 minutes to form a photosensitive layer with a thickness of 11 ⁇ m.
  • a layered substrate was obtained.
  • the content of solvent (e) in the photosensitive layer was 1.0% by mass.
  • thermocompression temperature 100° C.
  • thermocompression time 30 seconds
  • thermocompression pressure 0.3 MPa
  • the exposure mask used had thin lines in 1 ⁇ m increments with an opening width in the range of 5 to 40 ⁇ m. Further, as a sample for evaluating line width uniformity, an exposure mask having thin lines with the above-mentioned line widths was used in a total of 25 blocks, 5 blocks in each direction and 5 blocks in each direction. Further, as a sample for evaluating the disconnection probability, an exposure mask having the shape shown in FIG. 1 and having an opening with an opening width (L) of 40 ⁇ m and a length of 4.0 cm was used.
  • the substrate having the exposed photosensitive layer was immersed in a 0.2% by mass Na 2 CO 3 solution, and then rinsed with ultrapure water to obtain a ceramic green sheet substrate with a conductive pattern.
  • Table 1 shows the results evaluated by the method described above.
  • Examples 2-3 Comparative Example 1
  • Example 1 Manufacture of photosensitive layer-equipped substrate> was carried out in the same manner as in Example 1 except that the drying conditions were changed as shown in Table 1, and the solvent (e) content of the photosensitive layer was as shown in Table 1. Met.
  • a ceramic green sheet with a conductive pattern was obtained in the same manner as in Example 1. Table 1 shows the results evaluated by the method described above.
  • Examples 4 to 6, Comparative Example 2 instead of the ⁇ transfer step>, a ⁇ lamination step> is performed in which the base material of the substrate with a photosensitive layer is not peeled off, and instead of ⁇ exposure step A>, an exposure mask is brought into contact with the base material of the substrate with a photosensitive layer, and the base material is removed after exposure. Ceramic green sheets with conductive patterns were obtained in the same manner as in Examples 1 to 3 and Comparative Example 1, except that ⁇ exposure step B> in which the material was peeled off was used. Table 1 shows the results evaluated by the method described above.
  • Example 1 ⁇ Manufacture of a substrate with a photosensitive layer> was carried out in the same manner as in Example 1 except that the drying conditions were changed as shown in Table 1, and the solvent (e) content of the photosensitive layer was as shown in Table 1. Met. Using the obtained substrate with a photosensitive layer, a ceramic green sheet with a conductive pattern was obtained in the same manner as in Example 1. Table 1 shows the results evaluated by the method described above.
  • Example 1 ⁇ Manufacture of a substrate with a photosensitive layer> was carried out in the same manner as in Example 1 except that the drying conditions were changed as shown in Table 1, and the solvent (e) content of the photosensitive layer was as shown in Table 1. Met. Using the obtained substrate with a photosensitive layer, a ceramic green sheet with a conductive pattern was obtained in the same manner as in Example 1. Table 1 shows the results evaluated by the method described above.
  • Example 11-12 Example except that in ⁇ Preparation of photosensitive paste>, solvent e-2 was used instead of solvent e-1, and in ⁇ Preparation of substrate with photosensitive layer>, the drying conditions were changed as shown in Table 1.
  • the solvent (e) content of the photosensitive layer was as shown in Table 1.
  • Table 1 shows the results evaluated by the method described above.
  • a ⁇ lamination step> is performed in which the base material of the substrate with a photosensitive layer is not peeled off, and instead of ⁇ exposure step A>, an exposure mask is brought into contact with the base material of the substrate with a photosensitive layer, and the base material is removed after exposure.
  • Ceramic green sheets with conductive patterns were obtained in the same manner as in Examples 11 and 12, except that the material was peeled off in ⁇ Exposure Step B>. Table 1 shows the results evaluated by the method described above.
  • a photosensitive paste was directly applied onto the ceramic green sheet of the ceramic green sheet-equipped substrate and dried at a temperature of 120° C. for 4 minutes to form a photosensitive layer with a thickness of 11 ⁇ m.
  • the content of the solvent (e) in the photosensitive layer was as shown in Table 1.
  • a ceramic green sheet with a conductive pattern was obtained in the same manner as in Example 1 using the obtained base material of the substrate with a photosensitive layer. Table 1 shows the results evaluated by the method described above.
  • Ceramic green sheets with conductive patterns were obtained in the same manner as in Examples 1 and 2, except that in the ⁇ exposure step>, exposure was carried out without contacting the exposure mask. Table 1 shows the results evaluated by the method described above.

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  • Manufacturing Of Printed Wiring (AREA)
  • Producing Shaped Articles From Materials (AREA)
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Publication number Priority date Publication date Assignee Title
JP7640798B1 (ja) 2024-09-12 2025-03-05 ノリタケ株式会社 積層セラミック電子部品の内部電極用ペースト、および、積層セラミック電子部品の製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05212833A (ja) * 1991-11-29 1993-08-24 Asahi Chem Ind Co Ltd 薄膜状光重合性導電ペースト組成物積層体
JP2017182901A (ja) * 2016-03-28 2017-10-05 東レ株式会社 感光性導電ペースト及び、それを用いた電子部品の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05212833A (ja) * 1991-11-29 1993-08-24 Asahi Chem Ind Co Ltd 薄膜状光重合性導電ペースト組成物積層体
JP2017182901A (ja) * 2016-03-28 2017-10-05 東レ株式会社 感光性導電ペースト及び、それを用いた電子部品の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7640798B1 (ja) 2024-09-12 2025-03-05 ノリタケ株式会社 積層セラミック電子部品の内部電極用ペースト、および、積層セラミック電子部品の製造方法

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