WO2018012194A1 - Liant pour feuille crue, bouille comprenant ce liant, et feuille crue - Google Patents

Liant pour feuille crue, bouille comprenant ce liant, et feuille crue Download PDF

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Publication number
WO2018012194A1
WO2018012194A1 PCT/JP2017/022332 JP2017022332W WO2018012194A1 WO 2018012194 A1 WO2018012194 A1 WO 2018012194A1 JP 2017022332 W JP2017022332 W JP 2017022332W WO 2018012194 A1 WO2018012194 A1 WO 2018012194A1
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Prior art keywords
binder
green sheet
monomer
structural unit
weight
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PCT/JP2017/022332
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English (en)
Japanese (ja)
Inventor
淳美 種村
大輔 小法師
桐子 東
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日本エイアンドエル株式会社
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Priority to JP2017554548A priority Critical patent/JPWO2018012194A1/ja
Publication of WO2018012194A1 publication Critical patent/WO2018012194A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B35/6344—Copolymers containing at least three different monomers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • 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
    • 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
    • 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
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • 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 for a green sheet, a slurry containing the binder, and a green sheet.
  • a green sheet used for manufacturing a multilayer electronic component such as a multilayer ceramic capacitor is generally prepared by applying a slurry containing at least a ceramic powder, a binder, and a solvent to an object to be coated such as a film and drying it.
  • This green sheet is roughly classified into a water-based green sheet and an organic solvent-based green sheet depending on the type of solvent and binder used.
  • high integration, miniaturization, and weight reduction are rapidly progressing, and there is a growing need for high capacity and miniaturization of multilayer ceramic capacitors. Therefore, it is necessary to make the green sheet thinner, but water-based green sheets are more susceptible to environmental humidity than organic solvent-based green sheets.
  • stacking deviation is easily caused by deformation and elongation. Therefore, in recent years when miniaturization by sheet thinning and the like is desired, a high performance multilayer ceramic capacitor mainly using an organic solvent-based green sheet that does not have the disadvantages has been proposed.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 11-039943
  • Patent Document 2 proposes that a low-cost fixed pedestal can be formed by alternately performing green sheet formation and internal electrode pattern formation by thermal transfer printing.
  • Patent Document 3 X5R characteristics are satisfied using barium titanate, magnesium carbonate, yttrium oxide, chromium oxide, Mn 2 V 2 O 7 and a sintering aid, It has been proposed to obtain a dielectric composition with little change in dielectric constant with temperature.
  • JP 11-039943 A Japanese Patent Laid-Open No. 2004-119951 JP 2005-17914 A
  • an object of the present invention is to provide a binder for water-based green sheets that eliminates the disadvantages of water-based green sheets and organic solvent-based green sheets and can reduce the total cost.
  • an object of the present invention is to provide a binder for an aqueous green sheet characterized by containing a structural unit derived from an aliphatic conjugated diene monomer.
  • the green sheet using the water-based green sheet binder of the present invention can obtain a green sheet having the same physical properties as when the organic solvent-based green sheet slurry is used.
  • the green sheet of the present invention does not use an organic solvent as a slurry solvent unlike the organic solvent-based green sheet, there is a problem that the working environment is polluted by the organic solvent evaporated in the sheet manufacturing process, etc.
  • the problem that the factory environment is polluted by the discharged organic solvent can be avoided in advance, the cost for taking measures against these problems can be reduced, and the material cost related to the solvent can be reduced to reduce the sheet manufacturing cost .
  • the aqueous green sheet binder of the present invention contains a structural unit derived from an aliphatic conjugated diene monomer.
  • the binder for an aqueous green sheet in the present invention includes a structural unit derived from an aliphatic conjugated diene monomer as an essential component, and may further include another structural unit as an optional component.
  • Examples of the structural unit derived from the aliphatic conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1, Examples thereof include 3-butadiene, substituted linear conjugated pentadienes, substituted and side chain conjugated hexadienes, and the like, and one or more can be used. In particular, 1,3-butadiene is preferred.
  • the structural unit derived from the aliphatic conjugated diene monomer is preferably 5 to 85% by weight (the total of all monomers is 100% by weight), more preferably 10 to 70% by weight. If the amount is less than 5% by weight, the strength of the green sheet obtained without functioning as a binder tends to be inferior, and if it exceeds 85% by weight, the polymerization stability of the copolymer latex is inferior and the productivity increases such as an increase in aggregates. It tends to be inferior and is not preferred.
  • Other structural units include structural units derived from aromatic vinyl monomers, structural units derived from vinyl cyanide monomers, structural units derived from unsaturated carboxylic acid alkyl ester monomers, and functional units. Examples thereof include structural units derived from a monomer having a group, and these can be used alone or in combination of two or more. Among them, a structural unit derived from a monomer having a functional group, a structural unit derived from an aromatic vinyl monomer, a structural unit derived from a vinyl cyanide monomer, and / or an unsaturated carboxylic acid alkyl ester system By using a structural unit derived from a monomer, the balance between the sheet strength and the compatibility with other additives becomes good, and therefore it is preferable to combine them.
  • Examples of the structural unit derived from the aromatic vinyl monomer include styrene, ⁇ -methylstyrene, methyl- ⁇ -methylstyrene, vinyltoluene and divinylbenzene, and one or more types can be used. Styrene is particularly preferable.
  • Examples of the structural unit derived from the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile and the like, and one or more of them can be used. In particular, acrylonitrile and methacrylonitrile are preferable.
  • Structural units derived from unsaturated carboxylic acid alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate. And dimethyl itaconate, monomethyl fumarate, monoethyl fumarate, 2-ethylhexyl acrylate and the like, and one or more can be used. In particular, methyl methacrylate and butyl acrylate are preferable.
  • Examples of the structural unit derived from a monomer having a functional group include monomers having a carboxyl group, a hydroxyl group, and an amide group as the functional group, and an ethylene-based carboxylic acid monomer and a hydroxyl group-containing monomer. Examples thereof include saturated monomers and unsaturated carboxylic acid amide monomers, and these can be used alone or in combination of two or more.
  • Examples of the ethylenically unsaturated carboxylic acid monomer include mono- or dicarboxylic acids (anhydrides) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and the like. More than seeds can be used.
  • Examples of unsaturated monomers containing hydroxyl groups include ⁇ -hydroxyethyl acrylate, ⁇ -hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, and 3-chloro-2-hydroxypropyl methacrylate. , Di- (ethylene glycol) maleate, di- (ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis (2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate, etc. The above can be used. In particular, ⁇ -hydroxyethyl acrylate and ⁇ -hydroxyethyl methacrylate are preferable.
  • Examples of the unsaturated carboxylic acid amide monomer include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N, N-dimethylacrylamide, and the like, and one or more can be used. Particularly preferred are acrylamide and methacrylamide.
  • any of the monomers used in normal emulsion polymerization such as ethylene, propylene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, vinyl pyridine, chloroprene can be used. is there.
  • the structural unit derived from the aliphatic conjugated diene monomer and other structural units are preferably 5 to 95% by weight, more preferably 10 to 30% by weight (total of all monomers is 100% by weight). is there. By making it within this range, the balance between the sheet strength and the polymerization stability of the copolymer latex becomes better.
  • the polymerization method is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method may be used.
  • Emulsion polymerization is particularly preferred from the viewpoint of production efficiency because it is easy to obtain a high molecular weight substance, and the polymer is obtained as it is in a state dispersed in water, so that redispersion treatment is unnecessary.
  • aqueous green sheet binder In producing an aqueous green sheet binder by emulsion polymerization of the above monomers, conventional emulsifiers, polymerization initiators, reducing agents, chain transfer agents, crosslinking agents, redox catalysts, hydrocarbon solvents, electrolytes, A polymerization accelerator, a chelating agent, etc. can be used.
  • anionic surfactants such as sulfate esters of higher alcohols, alkylbenzene sulfonates, alkyl diphenyl ether disulfonates, aliphatic sulfonates, aliphatic carboxylates, sulfate esters of nonionic surfactants, etc.
  • nonionic surfactants such as an alkyl ester type, an alkyl phenyl ether type, and an alkyl ether type of polyethylene glycol, and one or more of these can be used.
  • alkylbenzene sulfonate and alkyl diphenyl ether disulfonate are preferable.
  • polymerization initiator examples include water-soluble polymerization initiators such as potassium persulfate, sodium persulfate, and ammonium persulfate, cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, An oil-soluble polymerization initiator such as 1,1,3,3-tetramethylbutyl hydroperoxide can be appropriately used.
  • water-soluble polymerization initiators such as potassium persulfate, sodium persulfate and ammonium persulfate and oil-soluble polymerization initiators of cumene hydroperoxide are preferred.
  • the reducing agent examples include sulfite, bisulfite, pyrosulfite, nitrite, nithionate, thiosulfate, formaldehyde sulfonate, benzaldehyde sulfonate, L-ascorbic acid, erythorbic acid, tartaric acid And carboxylic acids such as citric acid and salts thereof, further reducing sugars such as dextrose and saccharose, and amines such as dimethylaniline and triethanolamine.
  • L-ascorbic acid, erythorbic acid, and dextrose are preferable.
  • chain transfer agents examples include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan, dimethylxanthogen disulfide, diisopropylxanthogen disulfide, etc.
  • alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-stearyl mercaptan, dimethylxanthogen disulfide, diisopropylxanthogen disulfide, etc.
  • Xanthogen compounds tetramethylthiuram disulfide, tetraethylthiuram disulfide, thiuram compounds such as tetramethylthiuram monosulfide, phenol compounds such as 2,6-di-t-butyl-4-methylphenol, styrenated phenol, allyl alcohol Allyl compounds such as dichloromethane, dibromomethane, carbon tetrabromide, etc., ⁇ -benzyloxystyrene, ⁇ -benzyloxy In addition to vinyl ethers such as cyanacrylonitrile and ⁇ -benzyloxyacrylamide, terpinolene, triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexylthioglycolate, ⁇ -methylstyrene dimer, etc.
  • n-octyl mercaptan, t-dodecyl mercaptan, and ⁇ -methylstyrene dimer are preferable.
  • the amount of these chain transfer agents is not particularly limited, but is usually 0 to 5 parts by weight based on 100 parts by weight of the monomer.
  • the crosslinking agent is a structural unit derived from a crosslinkable monomer.
  • a crosslinkable monomer is a monomer that can form a crosslinked structure during or after polymerization by heating or energy irradiation.
  • a monomer having thermal crosslinkability can be usually mentioned. More specifically, a monofunctional monomer having a heat-crosslinkable crosslinkable group and one olefinic double bond per molecule, or a polyfunctional having two or more olefinic double bonds per molecule. May be used, and one kind or two or more kinds can be used.
  • thermally crosslinkable groups contained in the monofunctional monomer include epoxy groups, oxetanyl groups, oxazoline groups, and combinations thereof.
  • crosslinkable monomer having an epoxy group as a thermally crosslinkable group and having an olefinic double bond examples include vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, o-allylphenyl glycidyl.
  • Unsaturated glycidyl ethers such as ether; butadiene monoepoxide, chloroprene monoepoxide, 4,5-epoxy-2-pentene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxy-5,9-cyclododecadiene Monoepoxides of dienes or polyenes such as; alkenyl epoxides such as 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene; and glycidyl acrylate, glycidyl methacrylate, Glycidyl crotonate, Unsaturated carboxylic acids such as glycidyl-4-heptenoate, glycidyl sorbate, glycidyl linoleate, glycidyl-4-methyl-3-pentenoate, glycidyl este
  • crosslinkable monomer having an oxetanyl group as a thermally crosslinkable group and having an olefinic double bond examples include 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) Acryloyloxymethyl) -2-trifluoromethyloxetane, 3-((meth) acryloyloxymethyl) -2-phenyloxetane, 2-((meth) acryloyloxymethyl) oxetane, and 2-((meth) acryloyloxymethyl) ) -4-Trifluoromethyloxetane.
  • crosslinkable monomer having an oxazoline group as a heat crosslinkable group and having an olefinic double bond examples include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2- Oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline.
  • multifunctional monomers having two or more olefinic double bonds include allyl (meth) acrylate, ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, trimethylolpropane-tri (meth) acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane, trimethylolpropane-diallyl Ethers, allyl or vinyl ethers of polyfunctional alcohols other than those mentioned above, triallylamine, methylene bisacrylamide, and divinylbenzene.
  • unsaturated hydrocarbons such as pentene, hexene, heptene, cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene, 1-methylcyclohexene may be used.
  • cyclohexene which has a moderately low boiling point and can be easily recovered and reused after the completion of polymerization by steam distillation or the like, is preferable from the viewpoint of environmental problems although it differs from the object of the present invention.
  • anti-aging agents preservatives, dispersants, thickeners and the like can be appropriately added as necessary.
  • any one of single-stage polymerization, two-stage polymerization, multi-stage polymerization, seed polymerization method and the like may be adopted.
  • the addition method of various components in the polymerization is not particularly limited, and any of a batch addition method, a divided addition method, a continuous addition method, and a power feed method can be adopted.
  • the glass transition temperature (Tg) of the aqueous green sheet binder is not particularly limited, but is preferably ⁇ 60 to 90 ° C. If the glass transition temperature is less than ⁇ 60 ° C., it is difficult to maintain the sheet strength during handling, which is not preferable. When the glass transition temperature exceeds 90 ° C., the sheet strength is inferior, which is not preferable. More preferably, it is ⁇ 40 to 50 ° C.
  • the glass transition temperature can be measured by the following method.
  • Approx. 0.5 g of binder was applied to a glass plate and dried at 70 ° C. for 4 hours to form a film.
  • the dried film is set in an aluminum pan for DSC testing, and the sample is homogenized again by heating. Thereafter, the measurement temperature is increased from ⁇ 100 to 150 ° C. at a rate of 10 ° C./min, and the endothermic phase change is observed.
  • the starting point was read and used as the glass transition temperature (° C.) of the binder for aqueous green sheets.
  • the toluene-insoluble content (gel content) of the binder for water-based green sheets is not particularly limited, but is preferably 20% by weight or more, more preferably 40 to 99% by weight, and particularly preferably 60 to 98% by weight. If the toluene insoluble content is less than 20% by weight, it is difficult to maintain the sheet strength during handling, which is not preferable.
  • the method for measuring toluene insolubles is as follows.
  • ⁇ Binder is applied to a glass plate, and a film is produced in an atmosphere at a temperature of 80 ° C. Thereafter, about 1 g of the film is weighed, and this is placed in 400 ml of toluene and immersed for 48 hours. Thereafter, this is filtered through a 300-mesh wire mesh, and the toluene-insoluble portion captured by the wire mesh is dried, weighed, and calculated by weight% from the following formula.
  • Toluene insoluble content (toluene insoluble part weight) / (film weight before dissolution) ⁇ 100
  • the ash content (JIS K 0067-1992) of the binder for aqueous green sheets is, for example, 0% by mass or more, preferably 0.5% by mass or more, for example, 2.0% by mass or less, preferably 1.5% by mass. It is not more than mass%, more preferably not more than 1.0 mass%.
  • the content of metal elements (specifically, sodium, potassium, iron) in the aqueous green sheet binder is, for example, 0% by mass or more, preferably 0.1% by mass or more, more preferably Is 0.2% by mass or more, for example, 1.0% by mass or less, preferably 0.75% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.3% by mass. % Or less.
  • the amount of metal elements can be measured or calculated as a theoretical value.
  • the binder for an aqueous green sheet is thermally decomposed with sulfuric acid and nitric acid, and the mass of the metal element in the binder for the aqueous green sheet is determined by inductively coupled plasma emission spectroscopic analysis. And the mass of the obtained metal element is computed as a percentage with respect to solid content of the binder for water based green sheets.
  • the mass ratio of the metal element contained in each raw material is calculated from the molecular weight and chemical composition of each raw material containing the metal element. Next, all the products of the blending ratio of each raw material and the corresponding mass ratio are totaled.
  • the amount of the metal element is almost the same when measured and when calculated as a theoretical value.
  • the slurry for aqueous green sheets of the present invention contains the binder for aqueous green sheets of the present invention and ceramic.
  • the ceramic used in the slurry for the aqueous green sheet of the present invention known ceramics can be used and are not particularly limited.
  • barium titanate is preferably used.
  • the amount of the ceramic powder is too small, the viscosity of the slurry will be low, so the handling properties when molding the sheet will be poor, and if it is too large, the viscosity of the slurry will be high. Since dispersibility deteriorates, 30 to 80% by weight (in terms of solid content) in the total slurry is preferable.
  • the resulting green sheet has insufficient flexibility and strength, and cracks and the like are likely to occur after sintering, and if too large, the viscosity of the slurry is high. Therefore, the dispersibility of the ceramic powder and the like is lowered, so 3 to 20% by weight (in terms of solid content) in the total slurry is preferable.
  • a plasticizer In the water-based green sheet slurry of the present invention, a plasticizer, a dispersant, a lubricant, a wetting agent, an antistatic agent, an antifoaming agent, a drying accelerator and the like may be added as necessary.
  • the plasticizer is not particularly limited as long as it is compatible with the binder for water-based green sheets and is water-soluble, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, and hexamethylene glycol. It is done. These may be used alone or in combination of two or more.
  • the slurry for water-based ceramic green sheets of the present invention is defoamed as necessary, and then applied onto a support such as a peelable polyester film, water is removed by heating and drying, and then peeled off from the support. A green sheet is formed.
  • This green sheet can be used for ceramic electronic parts such as multilayer ceramic capacitors and ceramic circuit boards.
  • ceramic electronic parts such as multilayer ceramic capacitors and ceramic circuit boards.
  • green sheets are cut into a predetermined shape and size, electrodes are printed on the surface, then multiple sheets (several tens) are stacked, and then thermocompression bonded. To obtain a laminate. After cutting this into a suitable size, it is heated at a high temperature (for example, about 500 ° C.) to sinter ceramic powder and attach electrode terminals to obtain a multilayer ceramic capacitor.
  • a high temperature for example, about 500 ° C.
  • Ash content was measured according to JIS K 0067-1992.
  • aqueous green sheet 100 parts by weight of barium titanate as ceramic powder, 30 parts by weight of water, 0.5 part by weight of acrylic dispersant and 15 parts by weight of copolymer latex obtained in each example in terms of solid content
  • the mixture was mixed for 48 hours by a ball mill to obtain a slurry.
  • a green sheet having a thickness of 10 ⁇ m was prepared by a doctor blade method. The green sheet was dried at 100 ° C.
  • the tensile strength and elongation of the obtained green sheet were measured at 23 ° C. and a tensile speed of 10 mm / min with a tensile tester (manufactured by Minebea). Table 2 shows the results.
  • the green sheet using the water-based green sheet binder of the present invention can obtain a green sheet having the same physical properties as when the organic solvent-based green sheet slurry is used. Moreover, since the green sheet of the present invention does not use an organic solvent as a slurry solvent unlike the organic solvent-based green sheet, there is a problem that the working environment is contaminated by the organic solvent evaporated in the sheet manufacturing process, or from the factory. The problem that the factory environment is polluted by the discharged organic solvent can be avoided, the cost for taking measures against these problems can be reduced, and the material cost related to the solvent can be reduced, and the sheet manufacturing cost can be reduced. .
  • the water-based green sheet binder of the present invention is used to produce a green sheet used in the manufacture of multilayer electronic components such as multilayer ceramic capacitors.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Ceramic Capacitors (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)

Abstract

Selon l'invention, un liant pour feuille crue à base d'eau comprend une unité structurale dérivée d'un monomère à base de diène conjugué aliphatique.
PCT/JP2017/022332 2016-07-15 2017-06-16 Liant pour feuille crue, bouille comprenant ce liant, et feuille crue WO2018012194A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024095663A1 (fr) * 2022-10-31 2024-05-10 日本ゼオン株式会社 Composition en suspension pour couche diélectrique, couche diélectrique et condensateur
WO2024095664A1 (fr) * 2022-10-31 2024-05-10 日本ゼオン株式会社 Composition de liant pour couche diélectrique, composition de bouillie pour couche diélectrique, couche diélectrique et condensateur

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JP2005213064A (ja) * 2004-01-27 2005-08-11 Nitta Ind Corp セラミックス成形用バインダー、グリーン体、セラミックス成形体及びセラミックス接着法

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JP2005213064A (ja) * 2004-01-27 2005-08-11 Nitta Ind Corp セラミックス成形用バインダー、グリーン体、セラミックス成形体及びセラミックス接着法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024095663A1 (fr) * 2022-10-31 2024-05-10 日本ゼオン株式会社 Composition en suspension pour couche diélectrique, couche diélectrique et condensateur
WO2024095664A1 (fr) * 2022-10-31 2024-05-10 日本ゼオン株式会社 Composition de liant pour couche diélectrique, composition de bouillie pour couche diélectrique, couche diélectrique et condensateur

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