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  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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  • C04B35/638—Removal thereof
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  • B28—WORKING CEMENT, CLAY, OR STONE
  • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
  • B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
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  • C04B35/62605—Treating the starting powders individually or as mixtures
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  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
  • C04B35/62605—Treating the starting powders individually or as mixtures
  • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
  • C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
  • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
  • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
  • C04B35/632—Organic additives
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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
  • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
  • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
  • C04B35/632—Organic additives
  • C04B35/634—Polymers
  • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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  • C04B35/632—Organic additives
  • C04B35/634—Polymers
  • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
  • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/30—Stacked capacitors

Definitions

• the present disclosure relates to a method for removing an organic component from a ceramic molded body, an additive for producing a ceramic molded body, a binder solution for producing a ceramic molded body containing the additive, a ceramic slurry for producing a ceramic molded body, and a laminated ceramic capacitor. It relates to a manufacturing method.
• a binder resin such as polyvinyl butyral resin and a plasticizer are added to an organic solvent in which ceramic powder is dispersed, and a slurry composition for a ceramic green sheet is prepared by uniformly mixing with a ball mill or the like, and polyethylene terephthalate is prepared.
• a ceramic green sheet is manufactured by casting on a peelable support such as a film, distilling off the solvent and the like by heating or the like, and peeling from the support.
• the surface of the obtained ceramic green sheet is coated with a conductive paste to be an internal electrode by screen printing or the like, and a plurality of sheets are alternately stacked and thermocompression bonded to obtain a laminated body, which is cut into a desired size.
• a conductive paste to be an internal electrode by screen printing or the like
• a plurality of sheets are alternately stacked and thermocompression bonded to obtain a laminated body, which is cut into a desired size.
• the ceramic powder used in the ceramic green sheet has a fine particle diameter of 0.2 ⁇ m or less, and the thickness of the slurry composition containing the ceramic powder is 1 ⁇ m or less. Attempts have been made to apply a thin film on a releasable support.
• Patent Document 1 JP-A-2004-59358
• Patent Document 2 JP-A-2006-89354
• Patent Document 3 disclose binder resins for solving such problems.
• Patent Document 4 discloses a polymer dispersant that improves the dispersibility of ceramic powder. Further, in Japanese Patent Laid-Open No.
• Patent Document 5 in order to improve the debinding property and the sinterability, a predetermined substrate sintering of the green sheet for a substrate is performed on one side or both sides of the green sheet for a substrate.
• a method of manufacturing a ceramic electronic component in which a dummy green sheet made of a ceramic powder that does not sinter at a temperature, an oxide powder that serves as an oxidizing agent, and an organic binder is laminated.
• the oxide powder is at least one selected from the group consisting of lead dioxide, trilead tetraoxide, dilead trioxide, manganese dioxide, barium peroxide, calcium peroxide, strontium peroxide and zinc peroxide. It is disclosed.
• Patent Document 6 discloses a method for promoting combustion of an organic substance using a metal-containing substance containing a heavy metal selected from Ru, Pd, Os, Ir and Pt.
• Patent Document 7 discloses a ceramic green comprising a polyvinyl butyral resin and a methacrylic acid ester-based resin as main components, which are modified with an amide compound having an unsaturated bond. Sheet forming binders have been proposed.
• Patent Document 8 discloses a binder for forming a ceramic green sheet, which comprises a polyvinyl butyral resin and a methacrylic acid ester-based resin as main components, and a composite resin obtained by modifying these with ethylene carbonate. Proposed.
• barium titanate, niobium octylate, neodymium octylate, acetylacetone cobalt (III), ethyl silicate, raw materials containing acetylacetone manganese are pulverized, mixed and dispersed to obtain a mixed powder.
• the present disclosure is a method for removing an organic component from a ceramic molded body, which includes a step of holding a ceramic molded body containing an additive, a binder resin and a ceramic at a temperature of 200°C or higher and 500°C or lower.
• the present invention relates to a method for removing an organic matter component, which comprises at least one compound selected from salts with at least one inorganic acid (component A4).
• the present disclosure provides a compound having a ⁇ -diketone skeleton (component A1), a compound having an amine oxide group (component A2), a compound having a nitroxy radical group (component A3), and a transition metal ion and aluminum.
• An additive for producing a ceramic molded body comprising at least one compound selected from a salt of at least one of ions and an inorganic acid (component A4), wherein component A1 is bis(2,4-pentanedionato)manganese (II), tris(2,4-pentanedionato)iron(III), tris(2,4-pentanedionato)chromium(III), tris(2,4-pentanedionato)aluminum(III) and tris
• component A4 is bis(2,4-pentanedionato)manganese (II), tris(2,4-pentanedionato)iron(III), tris(2,4-pentanedionato)chromium(III), tris(2,4-pentanedionato)aluminum(III) and tris
• component A4 is bis(2,4-pentanedionato)manganese (II), tris(2,4-
• the present disclosure provides a compound having a ⁇ -diketone skeleton (component A1), a compound having an amine oxide group (component A2), a compound having a nitroxy radical group (component A3), and a transition metal ion and aluminum.
• a ceramic molded body containing an additive comprising at least one compound selected from a salt of at least one inorganic ion with an inorganic acid (component A4), a binder resin, and at least one solvent of an organic solvent and water.
• the present disclosure relates to a ceramic slurry for producing a ceramic molded body, which contains the additive of the present disclosure, a binder resin, a solvent of at least one of an organic solvent and water, and a ceramic.
• the present disclosure comprises a step of blending the additive of the present disclosure, a binder resin, a solvent of at least one of an organic solvent and water, and a ceramic to obtain a ceramic slurry, and a step of drying the ceramic slurry.
• the present invention relates to a method for manufacturing a ceramic molded body, which includes:
• the present disclosure relates, in one aspect, to a method for producing a ceramic molded body, including the steps of blending the binder solution of the present disclosure and a ceramic to obtain a ceramic slurry, and drying the ceramic slurry.
• a method for producing a monolithic ceramic capacitor comprising at least one compound selected from salts of at least one of a transition metal ion and an aluminum ion with an inorganic acid (component A4).
• the present disclosure has excellent removability of an organic component from a ceramic molded body, a method for removing an organic component, a ceramic molded body manufacturing additive, and a ceramic molded body manufacturing binder solution using the same, a ceramic slurry, Provided are a method for manufacturing a ceramic molded body and a method for manufacturing a laminated ceramic capacitor.
• the present disclosure is based on the finding that by manufacturing a ceramic green sheet using a specific additive, organic compounds derived from a binder resin or the like can be efficiently removed in the manufacturing process of a laminated ceramic capacitor.
• a method for removing an organic component from a ceramic molded body wherein the ceramic molded body containing an additive, a binder resin and a ceramic is maintained at a temperature of 200°C or higher and 500°C or lower.
• the additive comprises a compound having a ⁇ -diketone skeleton (component A1), a compound having an amine oxide group (component A2), a compound having a nitroxy radical group (component A3), a transition metal ion and
• the present invention relates to a method for removing an organic component, which comprises at least one compound selected from salts of aluminum ions with at least one inorganic acid (component A4).
• the present disclosure provides a compound having a ⁇ -diketone skeleton (component A1), a compound having an amine oxide group (component A2), a compound having a nitroxy radical group (component A3), and a transition metal ion and aluminum.
• component A1 a compound having a ⁇ -diketone skeleton
• component A2 a compound having an amine oxide group
• component A3 a compound having a nitroxy radical group
• transition metal ion and aluminum a transition metal ion and aluminum.
• additive of the present disclosure which is composed of at least one compound selected from salts of at least one of ionic and inorganic acids (component A4).
• the additive comprising at least one compound of the components A1 to A4 in the present disclosure is soluble in an organic solvent or water, it is uniformly dissolved even when added to a binder solution, becomes uniform in a ceramic slurry, and becomes a thin film support. Even if it is applied on top, it can be present uniformly in the ceramic compact.
• the components A1 to A4 function as oxidizing agents, it is presumed that organic substances such as a binder resin can be efficiently oxidized even at low temperatures, and organic substance residues can be reduced at low temperature and in a short time in the degreasing process and the firing process.
• the present disclosure need not be limited to these mechanisms.
• the present disclosure relates to a method of removing an organic component from a ceramic molded body (hereinafter, also referred to as “organic component removal method of the present disclosure”).
• the removal of organic components according to the present disclosure includes a step of holding a ceramic molded body containing an additive, a binder resin, and a ceramic at a temperature of 200° C. or higher and 500° C. or lower (hereinafter, also referred to as “degreasing step”). By maintaining this temperature range, it is considered that the decomposition of the organic matter is promoted while the sintering of the ceramic does not proceed, and the removal of the organic matter components proceeds efficiently.
• the holding temperature of the ceramic molded body in the degreasing step is 200° C. or higher, preferably 230° C. or higher, more preferably 250° C. or higher, in one or more embodiments, from the viewpoint of reducing organic residue, and the ceramic is From the viewpoint of preventing the occurrence of cracks in the molded body, it is preferably 500°C or lower, preferably 450°C or lower, and more preferably 400°C or lower.
• the holding temperature of the ceramic molded body in the degreasing step may be a constant temperature or a temperature change. Examples of the method of changing the temperature include a method of increasing the temperature from 200° C. to 500° C. at a low rate (continuous temperature increase).
• the rate of temperature increase is preferably 30° C./minute or less, more preferably 10° C./minute or less, and further preferably 5° C./minute or less, from the viewpoint of reducing organic residue.
• the rate of temperature increase is preferably 0.1° C./min or more from the viewpoint of reaching the ceramic firing temperature.
• the period for holding the ceramic molded body at a temperature of 200° C. or higher and 500° C. or lower is preferably 30 minutes or longer, more preferably 90 minutes or longer, further preferably 180 minutes or longer, from the viewpoint of reducing organic residue, Minutes or more is even more preferable.
• the period of maintaining the temperature is preferably 500 minutes or less from the viewpoint of improving the productivity of the fired ceramics.
• Examples of the ceramic molded body include ceramic green sheets.
• the additive contained in the ceramic molded body is, in one or more embodiments, a compound having a ⁇ -diketone skeleton (component A1), a compound having an amine oxide group (component A2), and nitroxy, from the viewpoint of reducing organic residue. It is composed of a compound having a radical group (component A3) and at least one compound selected from a salt of at least one of a transition metal ion and an aluminum ion with an inorganic acid (component A4). Examples of the components A1 to A4 include those described below.
• the binder resin contained in the ceramic molded body is preferably at least one compound selected from polyvinyl butyral resin, polyvinyl alcohol resin, and cellulosic resin from the viewpoint of reducing organic residue.
• the same ceramics (component E) used for preparing a ceramic slurry described later can be mentioned.
• the additive of the present disclosure is, in one or more embodiments, a compound having a ⁇ -diketone skeleton (component A1), a compound having an amine oxide group (component A2), a compound having a nitroxy radical group (component A3), And at least one compound selected from salts of at least one of transition metal ions and aluminum ions with an inorganic acid (component A4).
• the additive of the present disclosure in one or more embodiments, is an organic residue reducer.
• the additive of the present disclosure in one or more embodiments, is an oxidant for oxidizing organics.
• the additives of the present disclosure can be used, in one or more embodiments, to remove organic constituents from ceramic compacts.
• the compound having a ⁇ -diketone skeleton (component A1) in the present disclosure may be any compound as long as it has a ⁇ -diketone skeleton in the molecule.
• the component A1 may be one kind or a combination of two or more kinds.
• the component A1 may be partially or wholly in an enol form or an enolate form.
• the component A1 include at least one selected from the compound represented by the following formula (I) and the compound having a structure represented by the formula (II) in the molecule in one or more embodiments. From the viewpoint of reducing organic residue, a compound having a structure represented by formula (II) in the molecule is preferable.
• * indicates a bonding position. * Indicates a bonding position with a hydrogen atom or a metal element in one or more embodiments.
• the metal element include at least one selected from transition metals and aluminum.
• the transition metal include manganese, iron, cobalt, chromium and the like.
• the component A1 is preferably a complex (component A1′) of a compound having a ⁇ -diketone skeleton and at least one element selected from transition metals and aluminum from the viewpoint of reducing organic residue.
• the transition metal include first transition elements such as manganese, iron, cobalt and chromium. That is, the component A1 is preferably a complex (component A1′) of a compound having a ⁇ -diketone skeleton and at least one element selected from the first transition metal and aluminum, from the viewpoint of reducing organic residue.
• the present disclosure provides, in one aspect, a complex of a compound having a ⁇ -diketone skeleton and at least one element selected from a first transition metal and aluminum (component A1′), a compound having an amine oxide group (component A2). , A compound having a nitroxy radical group (component A3), and at least one compound selected from salts of at least one of transition metal ions and aluminum ions with an inorganic acid (component A4), an organic component from a ceramic molded body For use in the removal of.
• the present disclosure also provides, in one aspect, a complex of a compound having a ⁇ -diketone skeleton and at least one element selected from a first transition metal and aluminum (component A1′), a compound having an amine oxide group (component A2). At least one compound selected from the group consisting of: a compound having a nitroxy radical group (component A3), and a salt of at least one of a transition metal ion and an aluminum ion with an inorganic acid (component A4); It relates to its use as a manufacturing additive.
• component A1 examples include, in one or more embodiments, 1,3-cyclohexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, and bis(from the viewpoint of reducing organic residue.
• 2,4-Pentanedionate)manganese(II) Tris(2,4-pentanedionate)manganese(III), Tris(2,4-pentanedionate)iron(III), Bis(2,4-pentane) Dionato)cobalt(II), tris(2,4-pentanedionato)cobalt(III), tris(2,4-pentanedionato)chromium(III), tris(2,4-pentanedionato)aluminum( III), bis(2,4-pentanedionato)nickel(II), bis(2,4-pentanedionato)copper(II), tris(2,2,6,6-tetramethyl-3
• Component A1 is, in one or more other embodiments, bis(2,4-pentanedionato)manganese(II), tris(2,4-pentanedionato)iron(III), from the viewpoint of reducing organic residue. , Tris(2,4-pentanedionato)chromium(III), tris(2,4-pentanedionato)aluminum(III), and tris(2,2,6,6-tetramethyl-3,5-heptanedionato ) It is preferable that it is at least one compound selected from manganese (III).
• the compound having an amine oxide group (component A2) in the present disclosure may be any compound as long as it has an amine oxide group in the molecule.
• the component A2 may be one kind or a combination of two or more kinds.
• the component A2 is selected from a non-cyclic amine oxide compound represented by the following formula (III) and a cyclic amine oxide compound having a structure represented by the following formula (IV) or (V). At least one of
• R 1 , R 2 and R 3 each independently represent an organic group, and from the viewpoint of reducing organic residue, an alkyl group having 1 to 20 carbon atoms is preferable.
• the alkyl group may be linear or branched.
• R 4 represents a hydrocarbon group, and a methyl group is preferable from the viewpoint of reducing organic residue.
• R 5 and R 6 each independently represent a hydrogen atom or a hydrocarbon group.
• the hydrocarbon group is preferably a methyl group from the viewpoint of reducing organic residue.
• component A2 examples include N-methylmorpholine N-oxide, pyridine N-oxide, 2,6-lutizone N-oxide, trimethylamine N-oxide, and lauryldimethylamine N-oxide from the viewpoint of reducing organic residue. At least one selected is preferable, and N-methylmorpholine N-oxide is more preferable.
• the compound having a nitroxy radical group of the present disclosure may be any compound as long as it has a nitroxy radical group in the molecule.
• the component A3 may be one kind or a combination of two or more kinds.
• the component A3 includes, in one or more embodiments, a compound having a nitroxy radical represented by the following formula (VI) in the molecule.
• component A3 examples include 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, and At least one selected from 2-azaadamantane-N-oxyl and 2-hydroxy-2-azaadamantane is preferable, and 2,2,6,6-tetramethylpiperidine 1-oxyl and 4-hydroxy-2,2 At least one selected from 6,6-tetramethylpiperidine 1-oxyl is more preferable, and 2,2,6,6-tetramethylpiperidine 1-oxyl is further preferable.
• the components A1 to A3 preferably have a solubility in a mixed solvent of toluene and ethanol (mass ratio 1:1) of 1% by mass or more at 25° C. from the viewpoint of reducing organic residue.
• Component A4 is preferably at least one compound selected from iron nitrate, iron bromide, copper nitrate, copper chloride, and aluminum nitrate from the viewpoint of reducing organic residue. Since all the compounds of component A4 are soluble in water, it is preferable to use water as the solvent.
• Component A is, in one or more embodiments, bis(2,4-pentanedionato)manganese(II), tris(2,4-pentanedionato)iron(III), tris, from the viewpoint of reducing organic residue.
• the present disclosure relates to an additive composition (hereinafter, also referred to as “additive composition of the present disclosure”) containing an additive of the present disclosure (hereinafter, also referred to as “component A”).
• component A an additive of the present disclosure
• the above-mentioned thing is mentioned as a component A in the additive composition of this indication.
• the additive composition of the present disclosure can contain other components other than the component A in one or more embodiments. Examples of the other components include organic solvents.
• the present disclosure relates to a binder solution for producing a ceramic molded body (hereinafter, “binder solution of the present disclosure”) containing an additive (component A) of the present disclosure.
• the binder solution of the present disclosure includes the additive (component A) of the present disclosure, a binder resin (hereinafter, also referred to as “component B”), a solvent (at least one of an organic solvent and water) ( Hereinafter, also referred to as “component D").
• the binder solution of the present disclosure may further include a plasticizer (hereinafter, also referred to as “component C”) in one or more embodiments.
• component A is at least one selected from the component A1, the component A2 and the component A3, the binder solution of the present disclosure preferably contains the component C.
• the component A in the binder solution of the present disclosure includes the compound having the ⁇ -diketone skeleton (component A1), the compound having the amine oxide group (component A2), and the compound having the nitroxy radical group (component A3). ), and at least one compound selected from salts of at least one of transition metal ions and aluminum ions with an inorganic acid (component A4).
• the component A may be one kind or a combination of two or more kinds. Examples of the components A1 to A4 include those mentioned above. Among these, as the component A, the component A1 which is a compound having a structure represented by the above formula (II) is preferable from the viewpoint of reducing organic residue.
• the content of the component A in the binder solution of the present disclosure can be appropriately set according to the concentration of the component B.
• the content of the component A in the binder solution of the present disclosure is 0 from the viewpoint of reducing organic residue. 0.1% by mass or more is preferable, 0.3% by mass or more is more preferable, 0.5% by mass or more is further preferable, 0.8% by mass or more is further preferable, and 5% by mass or less from the same viewpoint. Is preferred, 4% by mass or less is more preferred, 3% by mass or less is more preferred, and 2% by mass or less is even more preferred.
• the content of the component A is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.3% by mass or more and 4% by mass or less, and 0.5% by mass or more and 3% by mass or less. Is more preferable, and 0.8% by mass or more and 2% by mass or less is even more preferable.
• the content of the component A means the total content thereof.
• the component B in the binder solution of the present disclosure has a low concentration (for example, the content of the component B is 8% by mass or less), the content of the component A in the binder solution of the present disclosure is from the viewpoint of reducing organic residue.
• 0.05 mass% or more is preferable, 0.1 mass% or more is more preferable, 0.2 mass% or more is further preferable, and from the same viewpoint, 5 mass% or less is preferable, and 4 mass% or less is more preferable. It is preferably 3% by mass or less, more preferably 2% by mass or less. More specifically, the content of the component A is preferably 0.05% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 4% by mass or less, and 0.2% by mass or more and 3% by mass or less. Is more preferable, and 0.2% by mass or more and 2% by mass or less is even more preferable.
• the content of the component A in the binder solution of the present disclosure is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and more preferably 5 parts by mass or more with respect to 100 parts by mass of the component B from the viewpoint of reducing organic residue. More preferably, 8 parts by mass or more is even more preferable. From the same viewpoint, with respect to 100 parts by mass of the component B, 40 parts by mass or less is preferable, 35 parts by mass or less is more preferable, 30 parts by mass or less is further preferable, and 25 parts by mass or less is further more preferable.
• the content of the component A is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 3 parts by mass or more and 35 parts by mass or less, and more preferably 5 parts by mass or more and 30 parts by mass with respect to 100 parts by mass of the component B. Parts or less are more preferable, and 8 parts by mass or more and 25 parts by mass or less are even more preferable.
• Component B in the binder solution of the present disclosure may be any binder resin that has been conventionally used for ceramic molded bodies such as ceramic green sheets.
• the component B may be one kind or a combination of two or more kinds.
• Specific examples of the component B include polyvinyl butyral resin (PVB resin), polyvinyl alcohol resin, cellulose resin, acrylic resin, vinyl acetate resin and the like.
• PVB resin polyvinyl butyral resin
• the component B at least one compound selected from a polyvinyl butyral resin, a polyvinyl alcohol resin and a cellulosic resin can be preferably used as the component B from the viewpoint of improving the strength of the ceramic molded body, and the polyvinyl butyral resin (PVB Resin) is preferred.
• the content of the component B in the binder solution of the present disclosure is preferably 5 mass% or more, more preferably 6 mass% or more, further preferably 8 mass% or more, and 10 mass% or more from the viewpoint of improving the strength of the ceramic molded body. Is more preferable, and from the viewpoint of reducing organic residues, 25% by mass or less is preferable, 20% by mass or less is more preferable, 18% by mass or less is further preferable, and 15% by mass or less is further more preferable. More specifically, the content of the component B is preferably 5% by mass or more and 25% by mass or less, more preferably 6% by mass or more and 20% by mass or less, further preferably 8% by mass or more and 18% by mass or less, and 10% by mass. % Or more and 15 mass% or less is still more preferable. When the component B is composed of two or more kinds of binder resins, the content of the component B means the total content thereof.
• the component C in the binder solution of the present disclosure may be any plasticizer that has been conventionally used for ceramic molded bodies such as ceramic green sheets.
• the component C may be one kind or a combination of two or more kinds.
• component C examples include dioctyl phthalate (DOP), dibutyl phthalate (DBP), bis(2-ethylhexyl)phthalate (DEHP) and other phthalic acid diesters, dioctyl adipate and other adipic acid diesters, and triethylene glycol.
• DOP dioctyl phthalate
• DBP dibutyl phthalate
• DEHP bis(2-ethylhexyl)phthalate
• other phthalic acid diesters dioctyl adipate and other adipic acid diesters
• triethylene glycol examples thereof include alkylene glycol diesters such as di2-ethyl hexalate, and bis(2-ethylhexyl) phthalate (DEHP) is preferable from the viewpoint of improving the flexibility of the ceramic molded body.
• the content of the component C in the binder solution of the present disclosure is preferably 0.5% by mass or more and 1% by mass or more from the viewpoint of improving the flexibility of the ceramic molded body. Is more preferable, 1.5% by mass or more is further preferable, 2% by mass or more is still more preferable, and from the viewpoint of reducing organic residue, 10% by mass or less is preferable, 7% by mass or less is more preferable, and 5% by mass is 5% by mass. The following is more preferable, and 4% by mass or less is even more preferable.
• the content of the component C is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 7% by mass or less, and further preferably 1.5% by mass or more and 5% by mass or less. It is more preferably 2% by mass or more and 4% by mass or less.
• the content of the component C means the total content thereof.
• the content of the component C is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, with respect to 100 parts by mass of the component B, from the viewpoint of flexibility of the ceramic molded body. 20 parts by mass or more is more preferable, and from the viewpoint of reducing organic residue, 50 parts by mass or less is preferable, 45 parts by mass or less is more preferable, and 40 parts by mass or less is further preferable, and 35 parts by mass is preferable. It is even more preferably less than or equal to parts by mass.
• the content of the component C is preferably 5 parts by mass or more and 50 parts by mass or less, more preferably 10 parts by mass or more and 45 parts by mass or less, and 15 parts by mass or more and 40 parts by mass with respect to 100 parts by mass of the component B.
• the amount is preferably not more than 20 parts by mass, more preferably not less than 20 parts by mass and not more than 35 parts by mass.
• Component D in the binder solution of the present disclosure may be any organic solvent or water that has been conventionally used for ceramic molded bodies such as ceramic green sheets.
• the component D may be one kind or a combination of two or more kinds.
• the binder solution of the present disclosure preferably contains an organic solvent as the component D.
• the binder solution of the present disclosure preferably contains water as the component D.
• Component D is an organic solvent
• specific examples of Component D include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-octanol, diacetone alcohol, terpineol, butyl carbitol.
• Alcohols such as; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone; N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl- Amides such as 2-pyrrolidone; Esters such as methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate; Ethers such as ethyl ether, dioxane, tetrahydrofuran; Hydrocarbons such as naphtha, n-hexane, cyclohexane; Aromatic compounds such as toluene, xylene and pyridine are listed, and from the viewpoint of improving the solubility of the binder resin, alcohols and cellosolves are preferable
• the component D is an organic solvent
• the component D is preferably a mixture of two or more kinds of organic solvents having different boiling points from the viewpoint of gently removing the organic solvent from the ceramic slurry to form a homogeneous ceramic molded body. More preferably, a mixture of the other organic solvent that is less likely to be azeotroped with the alcohols and the cellosolves, and the alcohols and the cellosolves.
• the other organic solvent that is less likely to be azeotroped with the alcohols and cellosolves hydrocarbons and aromatics are preferable, aromatics are more preferable, and toluene is further preferable.
• the component D a mixture of aromatics and alcohols is preferable, and a mixture of toluene and ethanol is more preferable.
• the mass ratio of toluene and ethanol (toluene/ethanol) in the organic solvent (component D) is preferably 0.1 or more and 3 or less, more preferably 0.3 or more and 2 or less, and 0.6 or more. 5 is more preferable.
• examples of the component D include distilled water, ion-exchanged water, pure water, and ultrapure water.
• the content of the component D in the binder solution of the present disclosure is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 65% by mass or more, and 70% by mass or more. Is more preferable, and from the viewpoint of improving productivity, 95% by mass or less is preferable, 90% by mass or less is more preferable, 88% by mass or less is further preferable, and 85% by mass or less is further more preferable. More specifically, the content of the component D is preferably 50% by mass or more and 95% by mass or less, more preferably 60% by mass or more and 90% by mass or less, further preferably 65% by mass or more and 88% by mass or less, 70% by mass. % To 85% by mass is even more preferable. When the component D is a mixture of two or more organic solvents, the content of the component D means the total content thereof.
• the binder solution of the present disclosure may further contain other components, if necessary, in addition to the components A to D.
• other components include conventionally known additives such as lubricants, dispersants and antistatic agents.
• the binder solution of the present disclosure is produced, for example, in one or a plurality of embodiments by blending the component A, the component B, the component D, and optionally the optional component (component C, other components) by a known method. it can. Therefore, in one aspect, the present disclosure relates to a method for producing a binder solution (hereinafter, also referred to as a “method for producing the binder solution of the present disclosure”) including a step of blending at least Component A, Component B, and Component D.
• “compounding” includes mixing the component A, the component B, the component D and, if necessary, the optional components (component C and other components) simultaneously or in any order.
• the blending amount of each component can be the same as the content of each component of the binder solution of the present disclosure described above.
• the present disclosure relates to a ceramic slurry for producing a ceramic molded body (hereinafter, also referred to as “ceramic slurry of the present disclosure”) containing the additive of the present disclosure.
• the ceramic slurry of the present disclosure includes the additive (component A) of the present disclosure, a binder resin (component B), a solvent (component D) of at least one of an organic solvent and water, and a ceramic ( Hereinafter, also referred to as "component E").
• component A is at least one selected from the component A1
• the component A2 and the component A3 the ceramic slurry of the present disclosure preferably contains an organic solvent as the component D.
• the ceramic slurry of the present disclosure preferably contains water as component D.
• the ceramic slurry of the present disclosure in one or more embodiments, can further include a plasticizer (component C).
• component A is at least one selected from the component A1, the component A2 and the component A3, the binder solution of the present disclosure preferably contains the component C.
• the content of the component A in the ceramic slurry of the present disclosure is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, from the viewpoint of reducing organic residue. More preferably, it is 8 mass% or more, and from the same viewpoint, 5 mass% or less is preferable, 4 mass% or less is more preferable, 3 mass% or less is further preferable, and 2 mass% or less is further more preferable. More specifically, the content of the component A is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.3% by mass or more and 4% by mass or less, and 0.5% by mass or more and 3% by mass or less. Is more preferable, and 0.8% by mass or more and 2% by mass or less is even more preferable. When the component A is composed of two or more compounds, the content of the component A means the total content thereof.
• the content of the component B in the ceramic slurry of the present disclosure is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 7% by mass or more, and 9% by mass or more from the viewpoint of improving the dispersibility of the ceramic. More preferably, and from the viewpoint of reducing organic residues, it is preferably 20% by mass or less, more preferably 18% by mass or less, still more preferably 15% by mass or less, still more preferably 12% by mass or less. More specifically, the content of the component B is preferably 2% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 18% by mass or less, further preferably 7% by mass or more and 15% by mass or less, and 9% by mass. % Or more and 12 mass% or less is still more preferable. When the component B is composed of two or more kinds of binder resins, the content of the component B means the total content thereof.
• the content of the component C in the ceramic slurry of the present disclosure is preferably 0.5% by mass or more and 1% by mass or more from the viewpoint of improving the flexibility of the ceramic molded body. More preferably, 1.5% by mass or more is further preferable, 2% by mass or more is still more preferable, and from the viewpoint of organic residue reduction, 9% by mass or less is preferable, 6% by mass or less is more preferable, and 4% by mass or less. Is more preferable and 3 mass% or less is still more preferable.
• the content of the component C is preferably 0.5% by mass or more and 9% by mass or less, more preferably 1% by mass or more and 6% by mass or less, and further preferably 1.5% by mass or more and 4% by mass or less. It is more preferably 2% by mass or more and 3% by mass or less.
• the content of the component C means the total content thereof.
• the content of the component D in the ceramic slurry of the present disclosure is preferably 45% by mass or more, more preferably 55% by mass or more, further preferably 60% by mass or more, and 65% by mass or more. Is more preferable, and from the viewpoint of improving productivity, 95% by mass or less is preferable, 90% by mass or less is more preferable, 85% by mass or less is further preferable, and 80% by mass or less is further more preferable. More specifically, the content of the component D is preferably 45% by mass or more and 95% by mass or less, more preferably 55% by mass or more and 90% by mass or less, further preferably 60% by mass or more and 85% by mass or less, and 65% by mass. % To 80% by mass is even more preferable. When the component D is composed of two or more organic solvents, the content of the component D means the total content thereof.
• the ceramic (component E) in the ceramic slurry of the present disclosure may be any ceramic as long as it has been conventionally used for a ceramic molded body such as a ceramic green sheet.
• the component E may be one kind or a combination of two or more kinds. Specific examples of the component E include alumina, silica, zirconia, titanium oxide, barium oxide, zinc oxide, magnesium oxide, aluminum silicate, barium titanate, strontium titanate, lead titanate, calcium titanate, sialon, spinemul.
• Examples of the powder include light, silicon carbide, silicon nitride, aluminum nitride, magnesium carbonate, barium carbonate, barium zirconate, calcium zirconate, and ferrite, and barium titanate is preferable from the viewpoint of improving the performance of the laminated ceramic capacitor.
• the barium titanate used in the ceramic slurry of the present disclosure is preferably powder from the viewpoint of improving dispersibility, improving the peelability of the ceramic molded body, and facilitating preparation of the ceramic slurry.
• the average particle diameter of the barium titanate based on the BET specific surface area (hereinafter, also simply referred to as “average particle diameter of barium titanate”) is preferably 5 nm or more, and 10 nm or more from the viewpoint of improving the releasability of the ceramic molded body.
• the average particle diameter of the barium titanate is preferably 5 nm or more and 300 nm or less, more preferably 10 nm or more and 200 nm or less, still more preferably 20 nm or more and 120 nm or less, still more preferably 35 nm or more and 100 nm or less.
• the average particle diameter based on the BET specific surface area of barium titanate used for preparing the ceramic slurry of the present disclosure is measured by a nitrogen adsorption method assuming that barium titanate is a sphere having a particle diameter R(m). It can be determined by using the obtained BET specific surface area S (m 2 /g) and the specific gravity ⁇ (6.0 g/cm 3 ) of barium titanate.
• the BET specific surface area is the surface area per unit mass
• S (m 2 /g) A (m 2 )
• the relational expression of is required.
• R(nm) 6000 ⁇ (S ⁇ )
• the average particle diameter (average particle diameter based on BET specific surface area) can be obtained. For example, if the BET specific surface area of barium titanate is 20 (m 2 /g), the average particle diameter (average particle diameter based on the BET specific surface area) is 50 nm.
• the content of the component E in the ceramic slurry of the present disclosure is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, and further preferably 13% by mass or more, from the viewpoint of improving electrical characteristics. From the viewpoint of improving coating workability and productivity, 80% by mass or less is preferable, 60% by mass or less is more preferable, 40% by mass or less is further preferable, and 30% by mass or less is further preferable. .. More specifically, the content of the component E is preferably 5% by mass or more and 80% by mass or less, more preferably 8% by mass or more and 60% by mass or less, still more preferably 10% by mass or more and 40% by mass or less, and 13% by mass. % Or more and 30 mass% or less is still more preferable. When the component E is composed of two or more kinds of ceramics, the content of the component E refers to the total content thereof.
• the ceramic slurry of the present disclosure may further contain other components, if necessary, in addition to the components A to E.
• other components include conventionally known additives such as lubricants, dispersants and antistatic agents.
• the ceramic slurry of the present disclosure is prepared by blending the component A, the component B, the component D, the component E and, if necessary, the optional component (component C, other components) by a known method. Can be manufactured. Moreover, since the binder solution of this indication contains the component A, the component B, the component D, and the component C as needed as above-mentioned, the ceramic slurry of this indication is other one or some embodiment.
• the binder solution of the present disclosure, the component E and, if necessary, other components can be prepared by blending by a known method.
• the organic solvent (component D) contained in the binder solution of the present disclosure may be a part of the organic solvent used for preparing the ceramic slurry of the present disclosure. That is, in the ceramic slurry of the present disclosure, in one or more other embodiments, the binder solution of the present disclosure, the organic solvent (component D), the component E and, if necessary, other components may be blended by a known method. Can be manufactured by. Therefore, in one aspect of the present disclosure, a step of blending the component A, the component B, the component D, the component E, and optionally the optional component (component C, other component) (hereinafter, also referred to as “blending step”).
• “compounding” includes mixing the component A, the component B, the component D, the component E and, if necessary, the optional components (component C, other components) simultaneously or in any order. From the viewpoint of reducing organic residues, it is preferable to mix the component A with the component E, the component D, and optionally other components, and then the component A. In one or a plurality of embodiments, the order of blending the component A includes mixing the component E and the component D, and then mixing a mixed solution containing the component A and the component B.
• the step of compounding the component E, the component D, and other components as necessary (primary dispersion process), the component A, the component B, and the components as the need arises.
• the step of further blending C (secondary dispersion step) is included.
• the ceramic slurry can be manufactured by crushing the component E to a primary particle size in a state where the component E, the component D, and the other components are mixed, and then mixing the component A, the component B, and the component C.
• the order of blending the component A includes mixing the component A immediately before forming the ceramic slurry into a film.
• the step of mixing the component E, the component D and the other component (primary dispersion step), and the component B and optionally the component C are further blended. It includes a step (secondary dispersion step) and a step of further blending the component A (final addition step).
• the blending amount of each component can be the same as the content of each component of the above-described ceramic slurry of the present disclosure.
• the solid content concentration of the ceramic slurry other than the organic solvent is diluted with an organic solvent (component D) from the viewpoint of improving workability and making the film thickness uniform. Is preferably 20% by mass or more and 40% by mass or less, and more preferably 25% by mass or more and 35% by mass or less.
• a method for producing the ceramic slurry of the present disclosure for example, a method of mixing the above components using various mixers such as a ball mill, a blender mill, and a three-roll mill can be mentioned.
• the present disclosure relates to a method for manufacturing a ceramic molded body (hereinafter, also referred to as a “method for manufacturing a ceramic molded body of the present disclosure”) including a step of drying a ceramic slurry of the present disclosure.
• a method for manufacturing a ceramic molded body according to the present disclosure an additive (component A) according to the present disclosure, a binder resin (component B), a solvent (component D) of at least one of an organic solvent and water, and a ceramic (component) are used.
• E) and optional components (component C and other components) are mixed as necessary to obtain a ceramic slurry, and a step of drying the ceramic slurry.
• a step of blending the binder solution of the present disclosure and a ceramic (component E) to obtain a ceramic slurry and a step of blending the ceramic slurry.
• a method for producing the ceramic molded body of the present disclosure in one or a plurality of embodiments, it can be produced by a conventionally known production method.
• the ceramic slurry of the present disclosure can be prepared by using a peelable support such as a polyethylene terephthalate film. Examples include a method in which the material is cast on the surface, the solvent and the like are distilled off by heating, and then the material is peeled from the support.
• the method for manufacturing a ceramic molded body of the present disclosure is preferably used for manufacturing a ceramic molded body which is a material for manufacturing a laminated ceramic capacitor.
• the monolithic ceramic capacitor can be produced by laminating a ceramic molded body, that is, a ceramic green sheet coated with a conductive paste.
• the present disclosure relates to a method for manufacturing a monolithic ceramic capacitor (hereinafter, also referred to as a “method for manufacturing a monolithic ceramic capacitor of the present disclosure”) including the organic component removal method of the present disclosure. That is, in one or a plurality of embodiments, the method for manufacturing a monolithic ceramic capacitor according to the present disclosure includes an additive (component A) including at least one compound selected from component A1, component A2, component A3, and component A4, and a binder resin. A step (degreasing step) of holding the ceramic molded body containing the (component B) and the ceramic (component E) at a temperature of 200° C. or higher and 500° C. or lower is included.
• the method for manufacturing a monolithic ceramic capacitor according to the present disclosure further includes a step (firing step) of firing the ceramic molded body after the degreasing step at a temperature exceeding 500° C. to obtain a fired ceramic product. .. Specifically, a plurality of sheets obtained by alternately coating the surface of a ceramic molded body (ceramic green sheet) containing component A, component B and component E with a conductive paste to be an internal electrode by screen printing or the like and thermocompression bonding. After obtaining a laminated body, cutting it to a desired size, and then thermally decomposing and removing organic components such as a binder resin contained in the laminated body by holding at a temperature of 200° C. or higher and 500° C. or lower (degreasing). Process), and the external electrodes are sintered on the end faces of the ceramic fired product obtained by firing at a temperature higher than 500° C., whereby a monolithic ceramic capacitor can be obtained.
• an organic solvent (component D) and a ceramic (component E) were mixed and stirred with a stirring rod to prepare a dispersion liquid of component E.
• 1 g of the ceramic slurries of Example 12 and Comparative Example 2 were prepared by blending and mixing each binder solution and the dispersion liquid of the component E.
• the content (% by mass, effective content) of each component in each ceramic slurry is as shown in Table 2.
• the numerical value in () shows content (mass %, effective component) of each component in the binder solution.
• ⁇ Binder (component B)> Polyvinyl butyral resin (PVB resin) [Kuraray Co., Ltd., Mobital B60H]
• ⁇ Plasticizer (component C)> Bis(2-ethylhexyl) phthalate [Fuji Film Wako Pure Chemical Industries, Ltd.]
• Organic solvent (component D)> Toluene [Fuji Film Wako Pure Chemical Industries, Ltd.]
• Ethanol [Fuji Film Wako Pure Chemical Industries, Ltd.]
• ⁇ Ceramic (component E)> Barium titanate [manufactured by Kyoritsu Material Co., Ltd., BT-HP9DX, average particle size 100 nm]
• TG (100%) at the start of measurement in Table 1 and Table 2 is the total mass of the additive (component A), binder (component B), plasticizer (component C), and ceramic (component E) at the start of measurement. is there.
• the value of TG (%) after the start of measurement decreases as the organic component contained in the evaluation film (molded product) is removed by heating, but becomes a constant value after the removal of the organic component is completed.
• the constant value depends on the components that do not decompose at the temperature during measurement (such as component E) and the mass of the organic residue.
• the period of 200° C. or more and 500° C. or less is 345.5 minutes. Further, the temperature of 50° C. to 200° C. is reached 7.5 minutes after the start of measurement.
• the ceramic slurries of Examples 1 to 11 have smaller TG (%) values than the ceramic slurries of Comparative Example 1, and the ceramic slurry of Example 12 is the ceramic of Comparative Example 2. Since the value of TG (%) was smaller than that of the rally, it was found that the amount of organic residue was small and the removability of organic components was excellent. Further, in the ceramic slurry of Example 12, the value of TG (%) after 200 minutes from the start of measurement reached the same value as the value after 300 minutes from the start of measurement and reached a constant value, while in the ceramic slurry of Comparative Example 2, Even after 300 minutes from the start of measurement, the TG (%) value decreased from the value 200 minutes after the start of measurement. From this, it was found that Example 12 also improved the removal rate of the organic component.
• Binder solutions of Examples 13 to 18 and Comparative Examples 3 to 4 were prepared by mixing and mixing Component A, Component B and Component D shown in Tables 3 to 4.
• the content (mass %, effective content) of each component in each binder solution is shown in Tables 3 to 4.
• TG (100%) at the start of measurement in Tables 3 to 4 is the total mass of the additive (component A4) and binder (component B) at the start of measurement
• TG (100% at the start of measurement in Table 5 ) Is the total mass of the additive (component A4), the binder (component B), and the ceramic (component E) at the start of the measurement.
• the value of TG (%) after the start of measurement decreases as the organic component contained in the evaluation film is removed by heating, but becomes a constant value after the removal of the organic component is completed.
• the constant value depends on the mass of components (component A4, component E, etc.) that are not decomposed at the temperature at the time of measurement.
• the period of time from 200° C. to 500° C. is 300 minutes. Further, the temperature of 50° C. to 200° C. is reached 150 minutes after the start of measurement.
• the binder solutions of Examples 13 to 16 have a smaller TG (%) value than the binder solutions of Comparative Example 3, less organic residue, and excellent removability of organic components. all right.
• the binder solutions of Examples 17 and 18 have a smaller TG (%) value than the binder solution of Comparative Example 4, and particularly a small TG (%) value after 400 minutes from the start of measurement. From the results, it was found that the amount of organic residue is small and the removal property of organic components is excellent.
• the ceramic slurries of Examples 19 to 21 have smaller TG (%) values than the ceramic slurries of Comparative Example 5, and the ceramic slurries of Example 22 have a smaller TG (%) value than the ceramic slurries of Comparative Example 6. Since the value of TG (%) was small, it was found that the amount of organic residue was small and the removal of organic components was excellent. Further, in Tables 3 to 5, the organic component reduction hardly progressed 100 minutes after the start of measurement (150°C) where the temperature did not reach 200°C, and 200 minutes after the start of measurement (250°C) where the temperature exceeded 200°C. It was found that the reduction of organic components is progressing.
• Example 23 The ceramic slurries of Examples 23 to 25 were prepared by changing the addition timing of the additive (component A). In Example 23, the additive (component A) was added in the secondary dispersion step, and in Example 24, the additive (component A) was added after the secondary dispersion step (final addition step). Then, it was added in the primary dispersion step.
• a specific method for preparing a ceramic slurry is shown below.
• Example 23 Polymer dispersing agent solution: 2.0 g and solvent: 45.7 g were weighed in a 1 L wide-mouthed plastic bottle, stirred well, then, ceramic (component E): 80.0 g was added, and ball mill stirring was performed using zirconia beads. Was carried out for 32 hours (primary dispersion step). Then 2.38 g of plasticizer (component C) was added. 250.6 g of solvent, 0.47 g of tris(2,4-pentanedionato)iron(III) (component A) and 9.09 g of binder (component B) were stirred for 32 hours in advance to add a mixed solution. Then, ball mill stirring was performed for 16 hours (secondary dispersion step).
• Example 24 Polymer dispersing agent solution: 2.0 g and solvent: 45.7 g were weighed in a 1 L wide-mouthed plastic bottle, stirred well, then, ceramic (component E): 80.0 g was added, and ball mill stirring was performed using zirconia beads. Was carried out for 32 hours (primary dispersion step). Then 2.38 g of plasticizer (component C) was added. 250.6 g of the solvent and 9.09 g of the binder (component B) were previously stirred for 32 hours to add a mixed solution which was a uniform solution, and the mixture was stirred by a ball mill for 16 hours (secondary dispersion step). Finally, 0.47 g of tris(2,4-pentanedionato)iron(III) (component A) was added and well stirred (final addition step).
• Example 25 Polymer dispersant solution: 2.0 g, solvent: 45.7 g, and tris(2,4-pentanedionato)iron(III) (component A) 0.47 g were weighed in a 1 L wide-mouthed plastic bottle, and after stirring well, , Ceramic (component E): 80.0 g was added, and the mixture was subjected to ball mill stirring for 32 hours using zirconia beads (primary dispersion step). Then 2.38 g of plasticizer (component C) was added. 250.6 g of the solvent and 9.09 g of the binder (component B) were previously stirred for 32 hours to add a mixed solution which was a uniform solution, and the mixture was stirred by a ball mill for 16 hours (secondary dispersion step).
• the polymer dispersant solutions used in the preparation of the ceramic slurries of Examples 23 to 25 were those synthesized as follows. ⁇ Synthesis of polymer dispersant> 60.0 g of ethanol was charged in advance in a 1 L 4-neck separable flask, and two dropping funnels, a reflux condenser, a thermometer, and a stirring device were attached. After purging with nitrogen, the temperature was raised to 80° C.
• stearyl methacrylate (NK Ester S: Shin-Nakamura Chemical Co., Ltd.): 30.0 g and methacrylic acid (Fuji Film Wako Pure Chemical Industries, Ltd.) ), 15.0 g, methoxy polyethylene glycol (23 mol) methacrylate (NK ester M-230G: manufactured by Shin-Nakamura Chemical Co., Ltd.): 155 g, mercaptopropanediol (chain transfer agent: Fuji Film Wako Pure Chemical Industries, Ltd.): 5.
• a mixed solution of 79 g and ethanol: 133.6 g and a mixed solution of V-65B (polymerization initiator: Fuji Film Wako Pure Chemical Industries, Ltd.): 4.43 g and ethanol: 106.4 g were separately added dropwise over 120 minutes. .. After the dropping was completed, the temperature was kept at 80° C. for 60 minutes and then cooled. The solid content concentration of the obtained polymer dispersant solution was 40.7% by mass, and the polystyrene reduced weight average molecular weight by GPC was 7,600.

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