WO2024095664A1 - Composition de liant pour couche diélectrique, composition de bouillie pour couche diélectrique, couche diélectrique et condensateur - Google Patents

Composition de liant pour couche diélectrique, composition de bouillie pour couche diélectrique, couche diélectrique et condensateur Download PDF

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WO2024095664A1
WO2024095664A1 PCT/JP2023/035967 JP2023035967W WO2024095664A1 WO 2024095664 A1 WO2024095664 A1 WO 2024095664A1 JP 2023035967 W JP2023035967 W JP 2023035967W WO 2024095664 A1 WO2024095664 A1 WO 2024095664A1
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dielectric layer
polymer
mass
binder composition
dielectric
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English (en)
Japanese (ja)
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智一 佐々木
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日本ゼオン株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • 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 invention relates to a binder composition for a dielectric layer, a slurry composition for a dielectric layer, a dielectric layer, and a capacitor. Regarding.
  • a capacitor such as a multilayer ceramic capacitor can generally be obtained by forming dielectric layers such as ceramic green sheets, stacking the dielectric layers, and optionally sintering them.
  • the dielectric layer can be obtained, for example, by first preparing a slurry composition containing a binder, a dielectric material, and a solvent, then applying the slurry composition onto a release substrate and then drying the slurry composition, and the obtained dielectric layer is then used to manufacture a capacitor.
  • Patent Document 1 proposes a binder for producing an inorganic sintered body, which contains a binder resin composition having a predetermined gel fraction and containing a predetermined composite resin, as a binder with excellent thermal decomposition properties that can produce a ceramic green sheet that can achieve a high porosity and is less likely to suffer from defects such as cracks when producing a sintered body, when used as a binder for producing a ceramic green sheet.
  • a dielectric layer such as a ceramic green sheet
  • it is usually rolled up together with the release substrate.
  • the dielectric layer is in close contact with the surface of the release substrate on the side on which the dielectric layer is not formed (hereinafter, sometimes referred to as the "rear surface of the release substrate"). If it is stored in this state, the dielectric layer may adhere to the rear surface of the release substrate (so-called blocking), which may cause the dielectric layer to break.
  • the present inventors have conducted extensive research with the aim of solving the above problems.
  • the present inventors have newly discovered that the above problems can be solved by using a binder composition for a dielectric layer that contains a polymer containing a specific monomer unit and a solvent, the polymer having a glass transition temperature equal to or higher than a specific temperature, and have completed the present invention.
  • an object of the present invention is to advantageously solve the above-mentioned problems, and [1] the present invention is a binder composition for a dielectric layer, comprising a polymer and a solvent, wherein the polymer contains a conjugated diene monomer unit and has a glass transition temperature of -45°C or higher.
  • the binder composition for a dielectric layer can impart excellent blocking resistance to the dielectric layer.
  • the binder composition for a dielectric layer can be used to prevent the dielectric layer formed on a release substrate from being unintentionally peeled off from the release substrate, i.e., to impart excellent adhesiveness to the dielectric layer.
  • the binder composition for the dielectric layer when the dielectric layer is peeled off from the release substrate after overlapping the dielectric layer with another layer and applying pressure during the production of a capacitor, the dielectric layer can be prevented from remaining on the release substrate.
  • excellent transferability can be imparted to the dielectric layer.
  • the glass transition temperature of a polymer can be measured according to the method described in the Examples.
  • the glass transition temperature is preferably 20° C. or lower.
  • the transferability of the dielectric layer can be improved.
  • the polymer preferably has a tetrahydrofuran insoluble content of 70 mass % or more.
  • THF tetrahydrofuran
  • the blocking resistance of the dielectric layer can be improved.
  • the THF insoluble content of the polymer can be measured according to the method described in the Examples.
  • the polymer is a particulate polymer, and the average particle size of the particulate polymer is 0.01 ⁇ m or more and 1.0 ⁇ m or less. If the polymer is a particulate polymer, the polymer can be uniformly dispersed in the dielectric layer when the dielectric layer is formed, thereby improving the performance of the dielectric layer. When the average particle size of the particulate polymer is equal to or greater than the above lower limit, the adhesiveness and transferability of the dielectric layer can be improved.
  • the average particle size of the particulate polymer is equal to or less than the above upper limit, the blocking resistance of the dielectric layer can be improved.
  • the average particle size of the particulate polymer can be measured according to the method described in the Examples.
  • the polymer further contains an aromatic vinyl monomer unit. If the polymer further contains an aromatic vinyl monomer unit, the blocking resistance of the dielectric layer can be improved.
  • the solvent is preferably water or an aqueous solvent. If the solvent is water or an aqueous solvent, the blocking resistance and transferability of the dielectric layer can be improved.
  • the content of the conjugated diene monomer unit is preferably 20% by mass or more and 60% by mass or less, when the total amount of the monomer units contained in the polymer is taken as 100% by mass.
  • the content of the conjugated diene monomer unit is equal to or more than the above lower limit, the adhesiveness and transferability of the dielectric layer can be improved.
  • the content of the conjugated diene monomer units is equal to or less than the above upper limit, the blocking resistance of the dielectric layer can be improved.
  • the content of various repeating units (monomer units) in the polymer can be measured by a nuclear magnetic resonance (NMR) method such as 1 H-NMR.
  • the present invention also aims to advantageously solve the above problems, and [8] the present invention is a slurry composition for a dielectric layer, comprising the binder composition for a dielectric layer according to any one of [1] to [7] above, and a dielectric material.
  • the use of the above-mentioned slurry composition for a dielectric layer can impart excellent blocking resistance to the dielectric layer.
  • the use of the above-mentioned slurry composition for a dielectric layer can impart excellent adhesion and transferability to the dielectric layer.
  • the present invention also aims to advantageously solve the above problems, and [9] the present invention is a dielectric layer obtained by drying a coating film made of the slurry composition for a dielectric layer according to [8] above.
  • the dielectric layer is easy to handle because it has excellent blocking resistance, adhesion and transferability, and as a result, capacitors can be produced efficiently.
  • Another object of the present invention is to advantageously solve the above problems, and the present invention is [10] a capacitor using the dielectric layer according to [9] above.
  • the capacitor has excellent productivity because it uses a dielectric layer that is easy to handle.
  • a binder composition for a dielectric layer that can impart excellent blocking resistance to the dielectric layer.
  • a slurry composition for a dielectric layer that can impart excellent blocking resistance to the dielectric layer.
  • a capacitor using the above-mentioned dielectric layer can be provided.
  • FIG. 1 is a schematic cross-sectional view showing an example of a multilayer ceramic capacitor as a capacitor of the present invention.
  • the binder composition for dielectric layer of the present invention (hereinafter, sometimes simply referred to as "binder composition”) can be used to prepare the slurry composition for dielectric layer of the present invention (hereinafter, sometimes simply referred to as "slurry composition").
  • the slurry composition of the present invention can be used to form a dielectric layer used in the manufacture of a capacitor or the like.
  • the dielectric layer of the present invention is formed by drying a coating film made of the slurry composition of the present invention.
  • the capacitor of the present invention is formed using a dielectric layer formed using the slurry composition of the present invention.
  • the binder composition for a dielectric layer of the present invention includes a polymer and a solvent, and may optionally include components other than the polymer and the solvent (hereinafter, may be referred to as "other components").
  • the polymer contains a conjugated diene monomer unit and has a glass transition temperature of -45°C or higher.
  • the binder composition generally does not contain a dielectric material, which will be described later.
  • the polymer contained in the binder composition of the present invention is a component that can function as a binder, and contains a conjugated diene monomer unit, and may optionally contain an aromatic vinyl monomer unit, an acid group-containing monomer unit, and a cyano group-containing monomer unit.
  • the polymer may also contain monomer units other than the conjugated diene monomer unit, the aromatic vinyl monomer unit, the acid group-containing monomer unit, and the cyano group-containing monomer unit (hereinafter, sometimes referred to as "other monomer units").
  • examples of polymers containing conjugated diene monomer units include copolymers containing aromatic vinyl monomer units and conjugated diene monomer units, such as styrene-butadiene copolymer (SBR), butadiene rubber (BR), isoprene rubber, acrylic rubber (NBR) (copolymers containing cyano group-containing monomer units and conjugated diene monomer units), and hydrogenated versions of these.
  • SBR styrene-butadiene copolymer
  • BR butadiene rubber
  • NBR acrylic rubber
  • the conjugated diene monomer unit is a monomer unit that can be formed by a conjugated diene monomer.
  • the conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted linear conjugated pentadiene, and substituted and side-chain conjugated hexadienes. These may be used alone or in combination of two or more. Among these, 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene) are preferred as the conjugated diene monomer, and 1,3-butadiene is more preferred.
  • the content of the conjugated diene monomer units is preferably 20% by mass or more, and more preferably 25% by mass or more, and is preferably 60% by mass or less, and more preferably 55% by mass or less, when all repeating units (all monomer units) contained in the polymer are taken as 100% by mass.
  • the content of the conjugated diene monomer unit is equal to or more than the above lower limit, the adhesiveness and transferability of the dielectric layer can be improved.
  • the content of the conjugated diene monomer units is equal to or less than the above upper limit, the blocking resistance of the dielectric layer can be improved.
  • the aromatic vinyl monomer unit is a monomer unit that can be formed by an aromatic vinyl monomer.
  • the aromatic vinyl monomer include styrene, ⁇ -methylstyrene, vinyltoluene, and divinylbenzene. These may be used alone or in combination of two or more. Among these, styrene is preferred as the aromatic vinyl monomer.
  • the content of the aromatic vinyl monomer unit is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 45% by mass or more, and is preferably 70% by mass or less, and more preferably 65% by mass or less, when all repeating units (all monomer units) contained in the polymer are taken as 100% by mass.
  • the content of the aromatic vinyl monomer unit is equal to or more than the above lower limit, the blocking resistance of the dielectric layer can be improved.
  • the content of the aromatic vinyl monomer unit is equal to or less than the above upper limit, the transferability of the dielectric layer can be improved.
  • the acid group-containing monomer unit is a monomer unit that can be formed by an acid group-containing monomer.
  • Examples of the acid group-containing monomer include an acid group-containing monomer and a sulfonic acid group-containing monomer.
  • Examples of the carboxylic acid group-containing monomer unit include monocarboxylic acids and their derivatives, dicarboxylic acids and their acid anhydrides, and their derivatives.
  • Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.
  • Examples of the monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, ⁇ -acetoxyacrylic acid, ⁇ -trans-aryloxyacrylic acid, ⁇ -chloro- ⁇ -E-methoxyacrylic acid, and the like.
  • the dicarboxylic acid includes maleic acid, fumaric acid, itaconic acid, and the like.
  • dicarboxylic acid derivatives include methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, and maleic acid monoesters such as butyl maleate, nonyl maleate, decyl maleate, dodecyl maleate, octadecyl maleate, and fluoroalkyl maleates.
  • maleic acid monoesters such as butyl maleate, nonyl maleate, decyl maleate, dodecyl maleate, octadecyl maleate, and fluoroalkyl maleates.
  • acid anhydrides of dicarboxylic acids include maleic anhydride, acrylic anhydride, methylmaleic anhydride, dimethylmaleic anhydride, and citraconic anhydride.
  • carboxylic acid group-containing monomer an acid anhydride which generates a carboxylic acid group upon hydrolysis can also be used.
  • carboxylic acid group-containing monomer ethylenically unsaturated polycarboxylic acids such as butene tricarboxylic acid, and partial esters of ethylenically unsaturated polycarboxylic acids such as monobutyl fumarate and mono-2-hydroxypropyl maleate can also be used.
  • sulfonic acid group-containing monomer examples include vinyl sulfonic acid (ethylene sulfonic acid), methyl vinyl sulfonic acid, (meth)allyl sulfonic acid, and 3-allyloxy-2-hydroxypropane sulfonic acid.
  • (meth)allyl means allyl and/or methallyl.
  • acrylic acid, methacrylic acid, itaconic acid and vinyl sulfonic acid are preferred, and acrylic acid, methacrylic acid and itaconic acid are more preferred.
  • the content of the acid group-containing monomer unit is preferably 0.1% by mass or more, and more preferably 0.2% by mass or more, and is preferably 10% by mass or less, and more preferably 5% by mass or less, when all repeating units (all monomer units) contained in the polymer are taken as 100% by mass.
  • the content ratio of the acid group-containing monomer unit is equal to or more than the above lower limit, the dispersion stability of the polymer in the binder composition and the slurry composition can be improved.
  • the content of the acid group-containing monomer unit is equal to or less than the above upper limit, the blocking resistance of the dielectric layer can be improved.
  • the cyano group-containing monomer unit is a monomer unit that can be formed by a cyano group-containing monomer.
  • Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more at any ratio. Among these, acrylonitrile is preferred as the cyano group-containing monomer.
  • the cyano group-containing monomer unit preferably accounts for 5% by mass or more, and more preferably 10% by mass or more, and preferably 25% by mass or less, and more preferably 20% by mass or less, when all repeating units (all monomer units) contained in the polymer are taken as 100% by mass.
  • the content of the cyano group-containing monomer unit is equal to or higher than the above lower limit, the blocking resistance of the dielectric layer can be improved.
  • the content of the cyano group-containing monomer unit is equal to or less than the above upper limit, the transferability of the dielectric layer can be improved.
  • the other monomer unit is a monomer unit that can be formed by another monomer.
  • the other monomer is not particularly limited as long as it is a monomer that can be copolymerized with the above-mentioned monomer.
  • Examples of the other monomer include amide group-containing monomers such as acrylamide and methacrylamide; crosslinkable monomers (crosslinkable monomers) such as allyl glycidyl ether, allyl (meth)acrylate, and N-methylolacrylamide; olefins such as ethylene and propylene; halogen atom-containing monomers such as vinyl chloride and vinylidene chloride; vinyl esters such as vinyl acetate, vinyl propionate, and vinyl butyrate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether; vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl ketone, and isopropenyl vinyl ketone; Examples of the other monomers include heterocycle-containing vinyl compounds such as N-vinylpyrrolidone, vinylpyridine, and vinylimidazole; amino group-containing monomers such as
  • (meth)acrylate means acrylate and/or methacrylate
  • (meth)acrylic means acrylic and/or methacrylic
  • the content of other monomer units is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and even more preferably 0% by mass, i.e., the polymer does not contain any other monomer units.
  • the glass transition temperature of the polymer must be ⁇ 45° C. or higher.
  • the glass transition temperature of the polymer is preferably ⁇ 30° C. or higher, more preferably ⁇ 25° C. or higher, and is preferably 20° C. or lower, more preferably 15° C. or lower. If the glass transition temperature of the polymer is ⁇ 30° C. or higher, the blocking resistance of the dielectric layer can be improved. On the other hand, if the glass transition temperature of the polymer is 20° C. or lower, the transferability of the dielectric layer can be improved.
  • the THF insoluble content of the polymer is preferably 70% by mass or more, more preferably 75% by mass or more, and is preferably 100% by mass or less, more preferably 98% by mass or less.
  • the THF insoluble content of the polymer is equal to or higher than the above lower limit, the blocking resistance of the dielectric layer can be improved.
  • the THF insoluble content of the polymer is equal to or less than the above upper limit, the adhesiveness and transferability of the dielectric layer can be improved.
  • the polymer contained in the binder composition of the present invention is preferably a particulate polymer. If the polymer is a particulate polymer, the polymer can be uniformly dispersed in the dielectric layer when the dielectric layer is formed, thereby improving the performance of the dielectric layer.
  • the average particle size of the particulate polymer is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and is preferably 1.0 ⁇ m or less, more preferably 0.8 ⁇ m or less, and even more preferably 0.5 ⁇ m or less.
  • the average particle size of the particulate polymer is equal to or greater than the above lower limit, the adhesiveness and transferability of the dielectric layer can be improved.
  • the average particle size of the particulate polymer is equal to or less than the above upper limit, the blocking resistance of the dielectric layer can be improved.
  • the polymerization method of the polymer is not particularly limited, and may be any method such as solution polymerization, suspension polymerization, bulk polymerization, emulsion polymerization, etc.
  • the polymerization reaction may be addition polymerization such as ionic polymerization, radical polymerization, living radical polymerization, etc.
  • the polymerization solvent and additives such as emulsifiers, dispersants, polymerization initiators, and chain transfer agents that can be used in the polymerization may be general ones, and the amounts used may be the amounts generally used.
  • the solvent contained in the binder composition of the present invention is not particularly limited, and both water and organic solvents can be used.
  • the organic solvent for example, aqueous solvents such as lower alcohols such as methanol, ethanol, isopropanol, etc., and non-aqueous solvents such as methylbenzene (toluene), xylene, etc. can be used.
  • the solvent is preferably water or an aqueous solvent, since this can improve the blocking resistance and transferability of the dielectric layer, and is particularly preferably water, from the viewpoints of reducing the environmental load, safety, and ease of availability.
  • the binder composition of the present invention may contain other components.
  • the other components include the above-mentioned additives and viscosity modifiers used when polymerizing the polymer.
  • polyvinyl butyral and the like can be used as the viscosity modifier.
  • the solids concentration of the binder composition is preferably 20% by mass or more, and more preferably 30% by mass or more, and is preferably 60% by mass or less, and more preferably 50% by mass or less.
  • the binder composition of the present invention can be prepared by mixing the above-mentioned polymer, solvent, and any other components by a known method. Specifically, the binder composition can be prepared by mixing the above-mentioned components using a mixer such as a ball mill, a sand mill, a bead mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, a film mix, or a planetary mixer.
  • a mixer such as a ball mill, a sand mill, a bead mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, a film mix, or a planetary mixer.
  • the slurry composition for dielectric layer of the present invention contains the binder composition of the present invention described above and a dielectric material. That is, the slurry composition of the present invention contains a polymer, a solvent, and a dielectric material.
  • the solvent contained in the slurry composition may be entirely derived from the binder composition, or may be newly added to the slurry composition separately from the solvent derived from the binder composition.
  • the slurry composition of the present invention may contain components other than the polymer, the solvent, and the dielectric material (hereinafter, may be referred to as "other components").
  • the slurry composition of the present invention contains the binder composition of the present invention, and therefore can impart excellent blocking resistance to the dielectric layer. Also, the slurry composition of the present invention contains the binder composition of the present invention, and therefore can impart excellent adhesion and transferability to the dielectric layer.
  • the dielectric material is not particularly limited as long as it is a material having dielectric properties, but it is preferable to use a ceramic material.
  • the ceramic material include zirconia, aluminum silicate, titanium oxide, zinc oxide, barium titanate, calcium zirconate, calcium titanate, strontium titanate, magnesia, sialon, spinemullite, silicon carbide, silicon nitride, and aluminum nitride. These ceramic materials may be used alone or in combination of two or more.
  • the ceramic material is preferably a ceramic material having a perovskite structure represented by the general formula ABO 3 as the main phase.
  • the ceramic material include barium titanate (BaTiO 3 ), calcium zirconate (CaZrO 3 ), calcium titanate (CaTiO 3 ), strontium titanate (SrTiO 3 ), and Ba 1-x-y Ca x Sr y Ti 1-z Zr z O 3 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1) which forms a perovskite structure.
  • barium titanate is preferable as the ceramic material having a perovskite structure as the main phase.
  • the average particle size of the dielectric material is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, even more preferably 0.05 ⁇ m or more, even more preferably 0.08 ⁇ m or more, and is preferably 1 ⁇ m or less, more preferably 0.8 ⁇ m or less, even more preferably 0.5 ⁇ m or less, even more preferably 0.3 ⁇ m or less, and even more preferably 0.2 ⁇ m or less.
  • the average particle size of the dielectric material means a particle size at which the cumulative volume calculated from the small diameter side is 50% in a particle size distribution (volume basis) obtained by measurement using a laser diffraction method.
  • the content of the dielectric material in the slurry composition is preferably 40% by mass or more, more preferably 50% by mass or more, and preferably 80% by mass or less, and more preferably 70% by mass or less, assuming that all components in the slurry composition (including the solvent) are 100% by mass.
  • solvent contained in the slurry composition of the present invention include the same solvents as those explained in the section "Solvent" of the above "Binder composition for dielectric layer”.
  • the content (solid content) of the viscosity modifier in the slurry composition is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, based on 100 parts by mass of the dielectric material in the slurry composition.
  • the solids concentration of the slurry composition is preferably 20% by mass or more, more preferably 25% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less.
  • the polymer content (solid content) in the slurry composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 7 parts by mass or less, based on 100 parts by mass of the dielectric material in the slurry composition.
  • the above-mentioned slurry composition can be prepared by mixing the above-mentioned components by a known mixing method.
  • Examples of the mixer used for the preparation include those listed in the above "Method for preparing the binder composition for the dielectric layer”.
  • the dielectric layer of the present invention is obtained by drying a coating film made of the above-mentioned slurry composition of the present invention.
  • the dielectric layer of the present invention is usually a dried film obtained by partially or completely removing the solvent from a coating film made of the above-mentioned slurry composition of the present invention. That is, the dielectric layer of the present invention contains the above-mentioned polymer and a dielectric material, and optionally contains a solvent and other components.
  • the dielectric layer of the present invention is obtained by drying a coating film made of the slurry composition of the present invention, and therefore has excellent blocking resistance, adhesion and transferability. Since the dielectric layer of the present invention has excellent blocking resistance, adhesion and transferability, it is easy to handle, and as a result, capacitors can be produced efficiently.
  • the content of the dielectric material in the dielectric layer is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more, and is preferably 98% by mass or less, and more preferably 95% by mass or less, assuming that all components in the dielectric layer are 100% by mass.
  • the polymer content in the dielectric layer is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 7 parts by mass or less, based on 100 parts by mass of the dielectric material in the dielectric layer.
  • the thickness of the dielectric layer is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, and is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the dielectric layer of the present invention may have a conductor layer formed thereon.
  • the conductor layer can be formed by various printing methods such as screen printing, gravure printing, stamp printing, inkjet printing, and offset printing using a pattern formed by these methods, or by a vacuum deposition method for forming a metal deposition film.
  • a conductive paste can be used.
  • the conductive paste can be prepared by a conventional method, for example, by mixing a conductive powder such as a metal, a dispersant, a plasticizer, a solvent, etc. with a polyvinyl acetal resin.
  • the dielectric layer can be produced by applying the slurry composition of the present invention onto a release substrate and drying the formed coating film.
  • the release substrate used in producing the dielectric layer is made of a resin having flexibility. Since the release substrate is made of a resin having flexibility, the release substrate (laminated film) on which the dielectric layer is formed by applying the slurry composition onto the release substrate and drying it can be stored in a rolled state and supplied as needed.
  • the release substrate is not particularly limited, and examples thereof include substrates containing resins such as polyesters, such as polyethylene terephthalate and polyethylene naphthalate, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, and polyvinyl chloride.
  • the release substrate is surface-treated on the side on which the dielectric layer of the present invention is formed in order to improve releasability.
  • the surface treatment include surface treatment using a release agent such as a silicone-based release agent, a fluorine-based release agent, or a wax-based release agent.
  • the thickness of the release substrate is not particularly limited, but is usually 20 ⁇ m or more and 100 ⁇ m or less.
  • the method for applying the slurry composition to the release substrate is not particularly limited, and examples include known application methods using an applicator or various roll coaters such as a gravure coater or a comma coater (registered trademark).
  • the method for drying the coating film formed on the release substrate is not particularly limited, and examples include known drying methods using a hot air dryer.
  • the drying conditions can be set appropriately depending on the solvent content in the coating film, the thickness of the coating film, etc., but the drying temperature is usually 80°C or higher and 150°C or lower, and the drying time is usually 3 minutes or higher and 60 minutes or lower.
  • the dielectric layer of the present invention When the dielectric layer of the present invention is used to manufacture a capacitor, multiple dielectric layers may be stacked and then heated and pressed, but the dielectric layer may be peeled off from the release substrate as described above either before or after stacking and heating and pressing the dielectric layers.
  • the capacitor of the present invention is formed using the dielectric layer of the present invention described above.
  • the capacitor of the present invention has excellent productivity because it uses a dielectric layer that is easy to handle.
  • examples of the capacitor of the present invention include a capacitor obtained by sintering a laminate formed by stacking dielectric layers (sintered product), and a capacitor obtained by not sintering a laminate formed by stacking dielectric layers (unsintered product).
  • An example of a capacitor obtained by sintering the above-mentioned laminate is a multilayer ceramic capacitor.
  • An example of a capacitor obtained without sintering the laminate is a laminated metallized film capacitor.
  • the multilayer ceramic capacitor as the capacitor of the present invention typically comprises a layered dielectric, layered internal electrodes, and external electrodes, and the dielectric is formed by sintering the stacked dielectric layers of the present invention.
  • An example of a multilayer ceramic capacitor as the capacitor of the present invention will be described below with reference to Figure 1.
  • FIG. 1 is a schematic cross-sectional view showing an example of a multilayer ceramic capacitor as a capacitor of the present invention.
  • the multilayer ceramic capacitor 10 shown in FIG. 1 has layered dielectrics 11 and layered internal electrodes 12 that are alternately stacked, and has a pair of external electrodes 13 on the outside of the dielectrics 11 and the internal electrodes 12.
  • One of the pair of internal electrodes 12 adjacent to each other along the stacking direction with the dielectric 11 sandwiched therebetween is electrically connected to one of the pair of external electrodes 13 inside the multilayer ceramic capacitor 10, and the other of the pair of internal electrodes 12 adjacent to each other along the stacking direction with the dielectric 11 sandwiched therebetween is electrically connected to the other of the pair of external electrodes 13 inside the multilayer ceramic capacitor 10.
  • the multilayer ceramic capacitor can be manufactured by any conventional method without any particular limitations.
  • a multilayer ceramic capacitor can be manufactured by stacking a plurality of dielectric layers of the present invention, each of which has a conductive layer that can become an internal electrode, so that the dielectric layers and conductive layers alternate, heating and pressing the stack to produce a laminate, pyrolyzing and removing the binder components and the like contained in the laminate (degreasing treatment), sintering the stack, and forming external electrodes on the end faces of the sintered ceramic product obtained by sintering.
  • the degreasing treatment is usually carried out in a nitrogen atmosphere at a temperature of 300° C. to 500° C.
  • the degreasing treatment time is usually 1 hour to 5 hours.
  • the binder component content of the laminate after the degreasing treatment is usually 50 ppm or less.
  • the degreased laminate is usually sintered in a reducing atmosphere such as H 2 --N 2 --H 2 O gas with an oxygen partial pressure of 10 -9 to 10 -12 MPa at a temperature of 1000° C. to 1500° C.
  • the sintering time for the laminate is usually 1 hour to 30 hours.
  • the external electrodes can be formed by applying an external electrode material to the end faces of the sintered ceramic body obtained by sintering and then baking the applied material, thereby obtaining a multilayer ceramic capacitor as shown in FIG.
  • Examples of materials for the external electrodes include Cu paste containing glass frit.
  • the baking is usually performed in a nitrogen atmosphere at a temperature of 500° C. to 1500° C.
  • the surfaces of the external electrodes may be plated with Ni, Sn, or the like.
  • the present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
  • “%” and “parts” expressing amounts are based on mass unless otherwise specified.
  • the ratio of a monomer unit formed by polymerizing a certain monomer in the polymer usually coincides with the ratio (feed ratio) of that monomer to all monomers used in the polymerization of the polymer, unless otherwise specified.
  • the glass transition temperature of the polymer the average particle size of the polymer (particulate), the THF insoluble content of the polymer, the blocking resistance, the transferability, and the adhesiveness were measured and evaluated by the following procedures.
  • ⁇ Glass transition temperature of polymer> The polymer dispersions (solutions) prepared in the Examples and Comparative Examples were dried for 3 days in an environment of 50% humidity and 25°C to obtain a film having a thickness of 1.0 mm. This film was dried at 60°C for 10 hours using a vacuum dryer. Thereafter, the glass transition temperature (°C) of the dried film was measured using a differential scanning calorimeter (DSC6220SII, manufactured by Nano Technology Co., Ltd.) in accordance with JIS K7121 under the conditions of a measurement temperature of -100°C to 180°C and a heating rate of 5°C/min.
  • DSC6220SII differential scanning calorimeter
  • ⁇ Average particle size of polymer (particulate)> The average particle size of the polymer was measured by a laser diffraction method as follows. First, a measurement sample was prepared by adjusting the solid content concentration of the dispersion of the polymer (particulate) prepared in the example to 0.1% by mass. Then, in the particle size distribution (volume basis) measured using a laser diffraction particle size distribution analyzer (manufactured by Beckman Coulter, Inc., product name "LS-230”), the particle size D50 at which the cumulative volume calculated from the small diameter side becomes 50% was taken as the average particle size.
  • LS-230 laser diffraction particle size distribution analyzer
  • the dielectric layer was peeled off from the release substrate with the dielectric layer produced in the examples and comparative examples, and the peeled dielectric layer was cut into a square with a width of 5 cm and a length of 5 cm to prepare a test piece.
  • a polyethylene terephthalate (PET) film was prepared, and the PET film and the test piece (dielectric layer) were overlapped and left at 40°C and a pressure of 10 kg/ cm2 for 24 hours. After leaving for 24 hours, the adhesion state (blocking state) of the dielectric layer to the PET film was visually confirmed, and the blocking resistance was evaluated according to the following criteria.
  • B The dielectric layer blocks to the PET film, but peels off.
  • C The dielectric layer blocks to the PET film, and does not peel off.
  • the release substrates with a dielectric layer produced in the Examples and Comparative Examples were cut into squares measuring 5 cm wide x 5 cm long to prepare test pieces. Two of the above test pieces were prepared, stacked on top of each other so that the dielectric layers faced each other, and pressed at 40° C. under a pressure of 5 kg/cm 2 for 10 seconds. Thereafter, the release substrate was peeled off from one of the test pieces, and the peeled state (transferability) of the dielectric layer was visually confirmed, and the transferability was evaluated according to the following criteria.
  • C The dielectric layers do not adhere to each other, and most of the dielectric layer remains on the surface of the release substrate.
  • the release substrate with the dielectric layer produced in the examples and comparative examples was cut into a rectangle of 10 mm wide x 100 mm long to prepare a test specimen.
  • Cellophane tape (specified in JIS Z1522) was attached to the dielectric layer of the test specimen.
  • the cellophane tape was fixed flat on the horizontal surface of a test stand, and one end of the release substrate was pulled in a direction perpendicular to the cellophane tape surface at a pulling speed of 10 mm/min to peel it off, and the stress at that time was measured. The measurement was performed three times, and the average value was calculated, which was taken as the peel strength and evaluated according to the following criteria.
  • a higher peel strength indicates better adhesion between the dielectric layer and the release substrate.
  • C Peel strength is less than 10 N/m
  • Example 1 Preparation of Polymer Dispersion (Binder Composition)> In a 5 MPa pressure vessel equipped with a stirrer, 33 parts of 1,3-butadiene (BD), 3.8 parts of itaconic acid (IA), and 63.2 parts of styrene (ST) as a monomer composition, 0.4 parts of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water, and 0.5 parts of potassium peroxodisulfate as a polymerization initiator were placed, thoroughly stirred, and then heated to 50° C. to initiate polymerization.
  • BD 1,3-butadiene
  • IA itaconic acid
  • ST styrene
  • ST styrene
  • the mixture was cooled to terminate the reaction, and a mixture containing a polymer was obtained.
  • the mixture containing the polymer was adjusted to pH 8 by adding 5% aqueous sodium hydroxide solution, and then the unreacted monomer was removed by heating and vacuum distillation.
  • the mixture was then cooled to 30° C. or less to obtain a dispersion containing the desired polymer (solvent: water).
  • the solid content of the dispersion was 40%.
  • the obtained dispersion was used to measure the glass transition temperature of the polymer, the average particle size of the polymer (particulate), and the THF insoluble content of the polymer. The results are shown in Table 1.
  • ⁇ Preparation of Slurry Composition 100 parts of barium titanate (manufactured by Sakai Chemical Industry Co., Ltd., "BT-01") having an average particle diameter (d50) of 0.1 ⁇ m as a dielectric material, 12.5 parts (5 parts in terms of solid content) of an aqueous solution of polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., BL-2H) as a viscosity modifier, and 20 parts of water as a solvent were mixed with 100 parts of zirconia beads (manufactured by Nikkato Co., Ltd.) having a particle diameter of 0.1 mm as mixing beads, using a bead mill (manufactured by Imex Co., Ltd., "RMB-01").
  • the slurry composition obtained above was applied to a release-treated film (PET38AL-5, manufactured by Lintec Corporation) having a width of 100 mm and a length of 100 mm, using a gravure coater, so that the thickness of the dielectric layer after drying was about 1.0 ⁇ m, and the film was dried at 100° C. for 5 minutes in the atmosphere to form a dielectric layer on the release substrate (ceramic green sheet method).
  • the obtained release substrate with the dielectric layer was used to evaluate blocking resistance, transferability, and adhesion. The results are shown in Table 1.
  • Example 2 In preparing the polymer dispersion, a monomer composition containing 50 parts of 1,3-butadiene (BD), 3.8 parts of itaconic acid (IA), 31.2 parts of styrene (St), and 15 parts of acrylonitrile (AN) was used, and the operations, measurements, and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.
  • BD 1,3-butadiene
  • IA itaconic acid
  • St 31.2 parts of styrene
  • AN acrylonitrile
  • Example 3 In the preparation of the polymer dispersion and the slurry composition, toluene was used as the solvent, specifically, the polymer dispersion and the slurry composition were prepared as follows, except that the operations, measurements, and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.
  • ⁇ Preparation of polymer dispersion (binder composition)> In a 5 MPa pressure vessel equipped with a stirrer, 33 parts of 1,3-butadiene (BD), 3.8 parts of itaconic acid (IA), and 63.2 parts of styrene (ST) as a monomer composition, 0.4 parts of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water, and 0.5 parts of potassium peroxodisulfate as a polymerization initiator were placed, thoroughly stirred, and then heated to 50° C. to initiate polymerization.
  • BD 1,3-butadiene
  • IA itaconic acid
  • ST styrene
  • the mixture was cooled to stop the reaction, and a mixture containing a polymer was obtained.
  • Toluene was added to the mixture containing the polymer, and unreacted monomers and ion-exchanged water were removed by heating and vacuum distillation to perform solvent replacement. After that, the mixture was cooled to 30° C. or less to obtain a dispersion containing the desired polymer (solvent: toluene).
  • the solid content of the dispersion was 40%.
  • Comparative Example 1 Except for using a solution containing a polymer consisting of a homopolymer of 1,3-butadiene (BD) (solvent: toluene) instead of the polymer dispersion, various operations, measurements, and evaluations were carried out in the same manner as in Example 3. The results are shown in Table 1. In Comparative Example 1, since the polymer was dissolved in toluene, the average particle size of the polymer was not measured.
  • BD 1,3-butadiene
  • the use of the polymer dispersion (binder composition) of the example can impart excellent blocking resistance to the dielectric layer.
  • a binder composition for a dielectric layer that can impart excellent blocking resistance to the dielectric layer.
  • a slurry composition for a dielectric layer that can impart excellent blocking resistance to the dielectric layer.
  • a capacitor using the above-mentioned dielectric layer can be provided.
  • Multilayer ceramic capacitor 11 Dielectric 12: Internal electrode 13: External electrode

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Abstract

Le but de la présente invention est de fournir une composition de liant pour une couche diélectrique, qui est capable de conférer une excellente résistance au blocage à la couche diélectrique. La présente invention est une composition de liant pour une couche diélectrique, ladite composition de liant comprenant un polymère et un solvant, le polymère contenant une unité monomère diène conjugué et ayant une température de transition vitreuse de -45 °C ou plus.
PCT/JP2023/035967 2022-10-31 2023-10-02 Composition de liant pour couche diélectrique, composition de bouillie pour couche diélectrique, couche diélectrique et condensateur WO2024095664A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006299253A (ja) * 2005-03-24 2006-11-02 Nippon Zeon Co Ltd 顔料分散液及び該顔料分散液を含有する塗被紙用組成物
JP2013168272A (ja) * 2012-02-15 2013-08-29 Jsr Corp 電極用バインダー組成物、電極用スラリー、電極、および蓄電デバイス
WO2018012194A1 (fr) * 2016-07-15 2018-01-18 日本エイアンドエル株式会社 Liant pour feuille crue, bouille comprenant ce liant, et feuille crue
WO2020189401A1 (fr) * 2019-03-15 2020-09-24 Dic株式会社 Film isolant, film adhésif et câble plat
WO2021084671A1 (fr) * 2019-10-31 2021-05-06 Ｔｐｒ株式会社 Liant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006299253A (ja) * 2005-03-24 2006-11-02 Nippon Zeon Co Ltd 顔料分散液及び該顔料分散液を含有する塗被紙用組成物
JP2013168272A (ja) * 2012-02-15 2013-08-29 Jsr Corp 電極用バインダー組成物、電極用スラリー、電極、および蓄電デバイス
WO2018012194A1 (fr) * 2016-07-15 2018-01-18 日本エイアンドエル株式会社 Liant pour feuille crue, bouille comprenant ce liant, et feuille crue
WO2020189401A1 (fr) * 2019-03-15 2020-09-24 Dic株式会社 Film isolant, film adhésif et câble plat
WO2021084671A1 (fr) * 2019-10-31 2021-05-06 Ｔｐｒ株式会社 Liant

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