Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B28—WORKING CEMENT, CLAY, OR STONE
  • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
  • B28B1/00—Producing shaped prefabricated articles from the material
  • B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
• • 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
  • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
  • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
  • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
• • 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
• • 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
  • 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
  • C04B35/63424—Polyacrylates; Polymethacrylates
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic 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
  • H01G4/002—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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0562—Solid materials
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a heat-decomposable binder composition for molding a green sheet, a slurry for molding a green sheet containing the composition, a green sheet formed by applying and drying the slurry on a substrate, and a method for producing the same. , And a device provided with the green sheet and a method for manufacturing the same.
• Ceramics are used as parts for ceramic circuit boards, multilayer ceramic capacitors, all-solid-state batteries, etc. because they have excellent properties such as strength, insulation, chemical resistance, dielectric properties, and piezoelectricity. These ceramic circuit boards and multilayer ceramic capacitors are often manufactured by a method generally called a green sheet method.
• the green sheet method is a method of forming a ceramic green sheet (hereinafter, also referred to as "green sheet") containing various ceramic powders and a binder as main components, printing wiring with a metal paste, and sintering the ceramic. This is a manufacturing technique for forming a metal composite.
• a resin such as acrylic resin, ethyl cellulose, or polyvinyl butyral is used as a binder.
• This binder is required to have characteristics such as improved dispersibility of ceramic powder and improved green sheet strength.
• a multilayer ceramic capacitor a plurality of ceramic green sheets coated with a metal paste as an internal electrode by screen printing or the like are stacked and heat-bonded to obtain a laminate.
• a so-called degreasing treatment an external electrode is sintered on the end face of the ceramic sintered body obtained by firing.
• it is also required to reduce the thermal decomposition residue in order to avoid adverse effects on the product characteristics (see Patent Documents 1 and 2). If organic matter remains in the capacitor, the performance will deteriorate, so the organic matter is removed by lengthening the firing time, but this causes a deterioration in productivity.
• some aspects of the present invention provide a binder composition for forming a green sheet, which has easy thermal decomposition properties and can realize high strength of the green sheet in the production of the green sheet.
• some aspects of the present invention provide a green sheet molding slurry containing the composition.
• some aspects of the present invention provide a green sheet having excellent degreasing property and processability, and a method for producing the green sheet.
• some aspects of the present invention provide a device manufactured from the green sheet and a method of manufacturing the device.
• the present invention has been made to solve at least a part of the above-mentioned problems, and can be realized as any of the following aspects.
• One aspect of the binder composition for forming a green sheet according to the present invention is Containing the polymer (A) and the liquid medium (B),
• the polymer (A) contains a repeating unit (a1) derived from an aromatic carboxylic acid having an ethylenically unsaturated group.
• the weight average molecular weight (Mw) of the polymer (A) is 100,000 or more.
• the aromatic carboxylic acid having an ethylenically unsaturated group can contain a compound represented by the following general formula (1).
• R 1 to R 5 are independently combined with a hydrogen atom, a carboxyl group, a hydroxyl group, a substituted or unsubstituted hydrocarbon group, or R 2 and R 3 and bonded to each other. Represents a part of a ring structure having 3 to 6 ring members, which is composed of carbon atoms. However, at least one of R 1 to R 5 is a substituted or unsubstituted hydrocarbon having an ethylenically unsaturated group. It is a hydrogen group.
• the polymer (A) is selected from the group consisting of a carboxyl group, a hydroxyl group, a nitrogen-containing functional group, a phosphorus atom, a sulfur atom, a chlorine atom, a bromine atom, an iodine atom, an alkali metal, an alkaline earth metal and a transition metal.
• the content ratio of the repeating unit (a2) derived from the ethylenically unsaturated monomer (excluding the aromatic carboxylic acid having an ethylenically unsaturated group and the polyalkylene glycol monomethacrylate) containing at least one of them in the structure is When the total of the repeating units contained in the polymer (A) is 100 parts by mass, it can be less than 5 parts by mass.
• the polymer (A) is a repeating unit (a3) derived from a methacrylic acid ester (excluding the repeating unit (a1) and the repeating unit (a2)) and a repeating unit (a5) derived from an aromatic vinyl compound. (Excluding the repeating unit (a1) and the repeating unit (a2)).
• a repeating unit (a3) derived from a methacrylic acid ester (excluding the repeating unit (a1) and the repeating unit (a2)) and a repeating unit (a5) derived from an aromatic vinyl compound. (Excluding the repeating unit (a1) and the repeating unit (a2)).
• the total of the repeating units contained in the polymer (A) is 100 parts by mass
• the total of the repeating units (a1), the repeating units (a3), and the repeating units (a5) is 90 parts by mass. It can be more than that.
• the binder composition for forming a green sheet In any aspect of the binder composition for forming a green sheet.
• the structure containing a sulfur atom, a nitrogen atom or a carboxyl group is an initiator terminal.
• the amount of the polymerization initiator to be introduced can be less than 1 part by mass.
• the binder composition for forming a green sheet In any aspect of the binder composition for forming a green sheet.
• the amount of the chain transfer agent used is less than 1 part by mass. it can.
• any aspect of the binder composition for forming a green sheet When differential scanning calorimetry (DSC) is performed on the polymer (A) in accordance with JIS K7121, an endothermic peak can be observed in the temperature range of ⁇ 40 ° C. to 80 ° C.
• DSC differential scanning calorimetry
• binder composition for molding a green sheet it can be used for molding an all-solid-state battery.
• One aspect of the green sheet molding slurry according to the present invention is It contains the binder composition for molding a green sheet according to any one of the above embodiments, inorganic particles, and a liquid medium.
• the inorganic particles can contain at least one element selected from lithium and titanium.
• One aspect of the green sheet according to the present invention is It is formed by applying and drying the slurry for forming a green sheet according to any one of the above on a base material.
• One aspect of the device according to the present invention is It is manufactured from the green sheet of the above aspect.
• One aspect of the method for producing a green sheet according to the present invention is The step of applying and drying the slurry for forming a green sheet according to any one of the above on a substrate is included.
• One aspect of the method for manufacturing a device according to the present invention is The device is manufactured through the method for manufacturing a green sheet according to the above aspect.
• the binder composition for forming a green sheet according to the present invention in the production of a green sheet, it is possible to have an easily thermally decomposable property and to realize a high strength of the green sheet.
• Binder composition for forming a green sheet contains a polymer (A) and a liquid medium (B).
• the binder composition for forming a green sheet according to the present embodiment can improve the heat-decomposability and the strength of the green sheet.
• each component contained in the binder composition for forming a green sheet according to the present embodiment will be described in detail.
• the binder composition for forming a green sheet according to this embodiment contains a polymer (A).
• the polymer (A) contains a repeating unit (a1) derived from an aromatic carboxylic acid having an ethylenically unsaturated group, and has a weight average molecular weight (Mw) of 100,000 or more.
• the polymer (A) contained in the binder composition for molding a green sheet according to the present embodiment may be in the form of latex dispersed in the liquid medium (B), or may be dissolved in the liquid medium (B). It may be in the state of being In any case, by using the polymer (A), the stability of the green sheet molding slurry (hereinafter, also simply referred to as “slurry”) produced by mixing with inorganic particles or the like becomes good. Moreover, it is preferable because the coating property of the slurry on the base material is improved.
• Repeating unit (a1) derived from an aromatic carboxylic acid having an ethylenically unsaturated group The polymer (A) contains a repeating unit (a1) derived from an aromatic carboxylic acid having an ethylenically unsaturated group (hereinafter, also simply referred to as “repeating unit (a1)”).
• the aromatic carboxylic acid having an ethylenically unsaturated group is preferably a compound represented by the following general formula (1).
• R 1 to R 5 are independently combined with a hydrogen atom, a carboxyl group, a hydroxyl group, a substituted or unsubstituted hydrocarbon group, or R 2 and R 3 and bonded to each other. It represents a part of a ring structure having 3 to 6 ring members, which is composed of carbon atoms. However, at least one of R 1 to R 5 is a substituted or unsubstituted hydrocarbon group having an ethylenically unsaturated group.
• aromatic carboxylic acid having an ethylenically unsaturated group examples include 2-methacryloyloxyethyl phthalic acid, trimellitic acid (2-methacryloyloxy) ethyl monoester, 4-vinylbenzoic acid and the like.
• 2-methacryloyloxyethyl phthalic acid having a carboxyl group at a position away from the hydrocarbon group having an ethylenically unsaturated group is preferable.
• the methacrylic skeleton can be easily maintained, and the formation of a thermally decomposable structure can be suppressed.
• These monomers may be used alone or in combination of two or more.
• the lower limit of the content ratio of the repeating unit (a1) is preferably 0.5 parts by mass, preferably 3 parts by mass, when the total amount of the repeating units contained in the polymer (A) is 100 parts by mass. It is more preferably parts, and particularly preferably 5 parts by mass.
• the upper limit of the content ratio of the repeating unit (a1) is preferably 80 parts by mass, preferably 60 parts by mass, when the total amount of the repeating units contained in the polymer (A) is 100 parts by mass. Is more preferable, and 40 parts by mass is particularly preferable.
• the polymer (A) contains the repeating unit (a1) in the above range, the polymer (A) is excellent in thermal decomposition property and the amount of organic residue in the degreasing step is reduced. In addition, the strength of the obtained green sheet is improved. Further, since the carboxyl group content in the polymer (A) is a suitable amount, the dispersibility of the inorganic particles in the slurry is also good.
• repeating unit polymer (A) may contain repeating units derived from other monomers copolymerizable with these as shown below.
• the polymer (A) is a carboxyl group, a hydroxyl group, a nitrogen-containing functional group, a phosphorus atom, a sulfur atom, a chlorine atom, a bromine atom, an iodine atom, an alkali metal, an alkaline earth metal and a transition metal (specified in the present specification).
• repeating unit (a2) Derived from the repeating unit (a2) (hereinafter, also simply referred to as “repeating unit (a2)”).
• Examples of the ethylenically unsaturated monomer containing a carboxyl group in the structure include mono- or mono- or such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, 2- (meth) acryloyloxyethyl succinic acid.
• Dicarboxylic acid can be mentioned. These monomers may be used alone or in combination of two or more.
• Examples of the ethylenically unsaturated monomer containing a hydroxyl group in the structure include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) butyl. ) Acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, glycerin mono (meth) acrylate, glycerindi (meth) acrylate and the like. These monomers may be used alone or in combination of two or more.
• Examples of the ethylenically unsaturated monomer containing a nitrogen-containing functional group in the structure include -NH such as vinylamine, allylamine, aminostyrene, 2- (tert-butylamino) ethyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate. 2 , -NHR or -NR 2 (R: alkyl group)-containing ethylenically unsaturated monomer in the structure; -CN groups such as acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile, vinylidene cyanide, etc.
• -NH such as vinylamine, allylamine, aminostyrene, 2- (tert-butylamino) ethyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoe
• Ethylene unsaturated monomer contained in the structure acrylamide, methacrylicamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylicamide, N, N-diethylacrylamide, N, N-diethylmethacrylate, An ethylenically unsaturated monomer containing amides such as N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylic amide, N-methylol methacrylic amide, N-methylol acrylamide, diacetone acrylamide, and maleic acid amide in the structure. Can be mentioned. These monomers may be used alone or in combination of two or more.
• Examples of the ethylenically unsaturated monomer containing a phosphorus atom in its structure include 2- (meth) acryloyloxyethyl phosphate, bis (2- (meth) acryloyloxyethyl phosphate), and 2- (meth) acryloyloxyethyl.
• Phosphoryl choline and the like can be mentioned. These monomers may be used alone or in combination of two or more.
• Examples of the ethylenically unsaturated monomer containing a sulfur atom in its structure include vinyl sulfonic acid, styrene sulfonic acid, allyl sulfonic acid, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, sulfobutyl (meth) acrylate, 2- Examples thereof include acrylamide-2-methylpropanesulfonic acid, 2-hydroxy-3-acrylamidepropanesulfonic acid, acrylamidetert-butylsulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, vinylthiophene and the like. These monomers may be used alone or in combination of two or more.
• Examples of the ethylenically unsaturated monomer containing a chlorine atom, a bromine atom or an iodine atom in the structure include vinyl chloride, 4- (chloromethyl) styrene, 2-bromoethyl (meth) acrylic acid, and (meth) acrylic acid 2,. Chlorine atom, bromine atom or iodine atom as a counter anion of a monomer having a basic functional group such as 3-dibromopropyl, pentabromobenzyl (meth) acrylate, trimethyl-2-methacryloyloxyethylammonium chloride and the like. Examples thereof include ethylenically unsaturated monomers contained in the structure. These monomers may be used alone or in combination of two or more.
• the content ratio of the repeating unit (a2) is preferably less than 5 parts by mass when the total amount of the repeating units contained in the polymer (A) is 100 parts by mass.
• the upper limit of the content ratio of the repeating unit (a2) is more preferably 3 parts by mass and 1 part by mass when the total amount of the repeating units contained in the polymer (A) is 100 parts by mass. Is particularly preferable.
• the content ratio of the repeating unit (a2) is within the above range, the influence of the polymer (A) on the thermal decomposability is small, and good degreasing property may be maintained. Further, since the functional group content in the polymer (A) is a suitable amount, the dispersibility of the inorganic particles in the slurry may be improved. Further, it is also preferable that the polymer (A) does not contain the repeating unit (a2).
• the polymer (A) refers to a repeating unit (a3) derived from a methacrylic acid ester (excluding the repeating unit (a1) and the repeating unit (a2); hereinafter, also simply referred to as “repeating unit (a3)”). It is preferable to contain it.
• methacrylate ester examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, and hexyl methacrylate.
• These monomers may be used alone or in combination of two or more.
• propylene glycol monomethacrylate is a hydroxyl group-containing monomer, it has a slight adverse effect on thermal decomposition. Therefore, it is exceptionally treated as a repeating unit (a3), not as the repeating unit (a2).
• the lower limit of the content ratio of the repeating unit (a3) is preferably 5 parts by mass, preferably 7 parts by mass, when the total amount of the repeating units contained in the polymer (A) is 100 parts by mass. It is more preferable to have 10 parts by mass, and it is particularly preferable to have 10 parts by mass.
• the upper limit of the content ratio of the repeating unit (a3) is preferably 99.5 parts by mass, preferably 70 parts by mass, when the total amount of the repeating units contained in the polymer (A) is 100 parts by mass. It is more preferably parts by mass, and particularly preferably 50 parts by mass.
• the glass transition temperature (Tg) of the polymer (A) becomes suitable, so that the strength and handleability of the obtained green sheet are improved. In some cases. In addition, the thermal decomposability of the polymer (A) may be improved, and a device having good properties may be obtained.
• the polymer (A) refers to a repeating unit (a4) derived from an acrylic acid ester (excluding the repeating unit (a1) and the repeating unit (a2); hereinafter, also simply referred to as “repeating unit (a4)”). It may be contained.
• acrylate ester examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, and hexyl acrylate.
• At least one selected from ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate and 2-acryloyloxyethyl phthalic acid is preferable, and n-butyl acrylate is preferable. Especially preferable.
• the lower limit of the content ratio of the repeating unit (a4) is preferably 0.5 parts by mass when the total amount of the repeating units contained in the polymer (A) is 100 parts by mass.
• the upper limit of the content ratio of the repeating unit (a4) is preferably 20 parts by mass, preferably 10 parts by mass, when the total amount of the repeating units contained in the polymer (A) is 100 parts by mass. Is more preferable, and 5 parts by mass is particularly preferable.
• the polymer (A) is a repeating unit (a5) derived from an aromatic vinyl compound (excluding the repeating unit (a1) and the repeating unit (a2). Hereinafter, it is also simply referred to as “repeating unit (a5)”). May be contained.
• aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, divinylbenzene and the like. Among these, styrene and ⁇ -methylstyrene are preferable.
• the lower limit of the content ratio of the repeating unit (a5) is preferably 0 parts by mass and 5 parts by mass when the total amount of the repeating units contained in the polymer (A) is 100 parts by mass. It is more preferable to have 10 parts by mass, and it is particularly preferable to have 10 parts by mass.
• the upper limit of the content ratio of the repeating unit (a5) is preferably 50 parts by mass, preferably 30 parts by mass, when the total amount of the repeating units contained in the polymer (A) is 100 parts by mass. Is more preferable, and 20 parts by mass is particularly preferable.
• the total amount of the repeating unit (a1), the repeating unit (a3) and the repeating unit (a5) is 90 parts by mass.
• the above is preferable, 92 parts by mass or more is more preferable, and 95 parts by mass or more is particularly preferable.
• the polymer (A) exhibits good thermal decomposability and a green sheet having good degreasing property. Therefore, the characteristics of the device are likely to be improved.
• the weight average molecular weight (Mw) of the polymer (A) is 100,000 or more, preferably 300,000 or more, more preferably 300,000 or more when measured by size exclusion chromatography (SEC) conforming to JIS K7252. Is over 500,000.
• the upper limit of the weight average molecular weight (Mw) of the polymer (A) is preferably 5,000,000 or less, more preferably 4,000,000 or less, and particularly preferably 3,500,000 or less. Is. When the weight average molecular weight (Mw) of the polymer (A) is in the above range, the strength of the green sheet can be increased, which is preferable.
• the polymer (A) preferably has only one endothermic peak in the temperature range of ⁇ 40 ° C. to 80 ° C. when differential scanning calorimetry (DSC) according to JIS K7121 is performed.
• the temperature of this endothermic peak (that is, the glass transition temperature (Tg)) is preferably in the range of -40 ° C to 80 ° C, more preferably in the range of -30 ° C to 70 ° C, and is preferably in the range of -20 ° C to 70 ° C. It is particularly preferably in the range of 50 ° C.
• the polymer (A) has only one endothermic peak in the DSC analysis and the peak temperature is in the above range, the obtained green sheet will have good flexibility and thermocompression bonding property. preferable.
• the viscosity of the polymer (A) at a solid content concentration of 10% depends on the solvent type, but is preferably 50 to 10,000 mPa ⁇ s, more preferably 50 to 8,000 mPa ⁇ s, 100. It is particularly preferably about 5,000 mPa ⁇ s.
• the viscosity of the polymer (A) at a solid content concentration of 10% is at least the above lower limit value, the dispersibility of the inorganic particles becomes good and a homogeneous slurry can be produced, which is preferable.
• the viscosity of the polymer (A) at a solid content concentration of 10% is not more than the above upper limit value, the coatability of the slurry is improved, which is preferable.
• the viscosity of the polymer (A) at a solid content concentration of 10% is a value measured at a temperature of 25.0 ° C. using a B-type viscometer in accordance with JIS Z8803.
• a B-type viscometer for example, "RB-80L” or “TVB-10” manufactured by Toki Sangyo Co., Ltd. can be used.
• Method for synthesizing polymer (A) The method for synthesizing the polymer (A) is not particularly limited, but is carried out in the presence of a known chain transfer agent, polymerization initiator, dispersant or the like in a solvent containing water as a main component. Suspension polymerization is preferred.
• chain transfer agent used in the synthesis of the polymer (A) include n-hexyl mercaptan, n-octyl mercaptan, tert-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-stearyl mercaptan and the like.
• Alkyl mercaptans such as dimethylxanthogen disulfide, diisopropylxanthogen disulfide; thiuram compounds such as turpinolene, tetramethylthium disulfide, tetraethylthiuram disulfide, tetramethylthium monosulfide; 2,6-di-tert-butyl-4.
• -Pharmon compounds such as methylphenol and styrene phenol; allyl compounds such as allyl alcohol; halogenated hydrocarbon compounds such as dichloromethane, dibromomethane and carbon tetrabromide; ⁇ -benzyloxystyrene, ⁇ -benzyloxyacrylonitrile, ⁇ -
• vinyl ether compounds such as benzyloxyacrylamide, triphenylethane, pentaphenylethane, achlorein, metaacrolein, thioglycolic acid, thioapple acid, 2-ethylhexylthioglycolate, ⁇ -methylstyrene dimer and the like can be mentioned.
• the ratio of the chain transfer agent used is preferably less than 1 part by mass, preferably less than 0.5 parts by mass, when the total of all the monomers used for the polymerization of the polymer (A) is 100 parts by mass. It is more preferable that it is present, and it is particularly preferable that it is not substantially contained. When the ratio of the chain transfer agent used is within the above range, the amount of organic residue in the green sheet degreasing step can be further reduced.
• polymerization initiator used in the synthesis of the polymer (A) include water-soluble polymerization initiators such as sodium persulfate, potassium persulfate, and ammonium persulfate; benzoyl peroxide, lauroyl peroxide, 2,2'.
• Oil-soluble polymerization initiators such as -azobis (2-methylpropionic acid) dimethyl, 2,2'-azobisisobutyronitrile, 4,4'-azobis (4-cyanovaleric acid); sodium bicarbonate, iron ( II)
• Oil-soluble polymerization initiators such as -azobis (2-methylpropionic acid) dimethyl, 2,2'-azobisisobutyronitrile, 4,4'-azobis (4-cyanovaleric acid); sodium bicarbonate, iron ( II)
• a redox-based polymerization initiator composed of a combination of a reducing agent such as a salt or a tertiary amine and an oxidizing agent such as a persulfate or an organic peroxide.
• These polymerization initiators may be used alone or in combination of two or more.
• the proportion of the polymerization initiator used is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the monomers used.
• the proportion of the polymerization initiator used is the same as that of the polymer (A).
• the total of all the monomers used for the polymerization is 100 parts by mass, it is preferably less than 1 part by mass, more preferably less than 0.5 parts by mass, and particularly preferably not substantially contained. ..
• the ratio of the polymerization initiator that introduces a structure containing a sulfur atom, a nitrogen atom or a carboxyl group as an initiator terminal is within the above range, the amount of organic residue in the green sheet degreasing step can be further reduced.
• dispersant used in the synthesis of the polymer (A) include polymer dispersants such as polyvinyl alcohol, polyacrylate, polymethacrylate, polyacrylamide, and cellulose derivatives, and anionic surfactants.
• Nonionic surfactants, amphoteric surfactants, fluorine-based surfactants and the like can be mentioned. These dispersants may be used alone or in combination of two or more.
• the proportion of the dispersant used is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass, based on 100 parts by mass of the total amount of the monomers used.
• the polymerization temperature at the time of synthesizing the polymer (A) is not particularly limited, but considering the production time and the conversion rate (reaction rate) of the monomer to the copolymer, 30 ° C. to 95 ° C. is preferable, and 50 ° C. to 85 ° C. Is more preferable. Further, at the time of polymerization, it is also possible to use a pH adjuster, EDTA, which is a metal ion encapsulant, or a salt thereof, for the purpose of improving production stability.
• EDTA which is a metal ion encapsulant, or a salt thereof
• the binder composition for forming a green sheet according to this embodiment contains a liquid medium (B).
• the liquid medium (B) include water, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, trimethylpentanediol monoisobutyrate, butyl carbitol, and butyl carbi.
• terpineol and isopropanol are preferable from the viewpoint of surface smoothness of the green sheet, and an aqueous medium containing water is preferable from the viewpoint of reducing the environmental load and the cost of manufacturing equipment. More preferably.
• the binder composition for molding a green sheet according to the present embodiment may contain additives other than the above-mentioned components, if necessary.
• additives include polymers other than the polymer (A), preservatives, thickeners, plasticizers, and the like.
• the binder composition for forming a green sheet according to this embodiment may contain a polymer other than the polymer (A).
• a polymer is not particularly limited, but is limited to polyacrylonitrile, polyethylene oxide, polypropylene oxide, polyvinyl chloride, polymethylmethacrylate, polymethylacrylate, polyvinylidene chloride, polyethyleneimine, polymethacrylonitrile, polyimide, polyamic acid.
• Polyamideimide polyester, polyethylene, polypropylene, polyvinyl acetate, nitrocellulose, polytetrafluoroethylene, ethylene-acrylic acid copolymer, (Na + ) ion cross-linked product of ethylene-acrylic acid copolymer, ethylene-methacrylic acid Copolymer, (Na + ) ion cross-linked product of ethylene-methacrylic acid copolymer, (Na +) ion cross-linked product of ethylene-methyl acrylate copolymer, (Na + ) ion cross-linked product of ethylene-methyl acrylate copolymer, ethylene-methacrylic acid Methyl copolymer, (Na + ) ion crosslinked product of ethylene-methyl methacrylate copolymer, polymer composed of monoalkyltrialkoxysilane polymer, copolymerization of monoalkyltrialkoxysilane polymer and tetraalkoxysi
• the content ratio of the polymer (A) in the binder composition for forming a green sheet according to the present embodiment is 100 parts by mass in total of the polymer (A), the polymer other than the polymer (A), and the thickener. It is preferably 10 to 100 parts by mass, more preferably 30 to 100 parts by mass, and particularly preferably 50 to 100 parts by mass.
• the binder composition for molding a green sheet according to the present embodiment may contain a preservative.
• a preservative By containing a preservative, when the binder composition for molding a green sheet is stored, it may be possible to suppress the growth of bacteria, mold and the like to generate foreign substances.
• Specific examples of the preservative include compounds described in Japanese Patent No. 5477610.
• the binder composition for forming a green sheet according to this embodiment may contain a thickener. By containing a thickener, the coatability thereof, the characteristics of the obtained device, and the like may be further improved.
• the thickener include cellulose compounds such as carboxymethyl cellulose, methyl cellulose, ethyl cellulose, and hydroxypropyl cellulose; poly (meth) acrylic acid; the cellulose compound or the ammonium salt or alkali metal salt of the poly (meth) acrylic acid.
• Polyvinyl alcohol-based (co) polymers such as polyvinyl alcohol, modified polyvinyl alcohol, and ethylene-vinyl alcohol copolymers; the common weight of unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, and fumaric acid with vinyl esters. Examples thereof include water-soluble polymers such as coalesced saponified compounds. Among these, it is preferable to select ethyl cellulose, an alkali metal salt of carboxymethyl cellulose, an alkali metal salt of poly (meth) acrylic acid, or the like according to the properties of the liquid medium (B).
• the content ratio of the thickener is preferably 5 with respect to 100 parts by mass of the total solid content of the binder composition for green sheet molding. It is not more than parts by mass, and more preferably 0.1 to 3 parts by mass.
• Green Sheet Molding Slurry contains the above-mentioned green sheet molding binder composition, inorganic particles, and a liquid medium.
• each component contained in the slurry for forming a green sheet according to the present embodiment will be described in detail.
• the content of the polymer (A) in the green sheet molding slurry according to the present embodiment is preferably 1 to 30% by mass, more preferably 2 to 25, when the total mass of the slurry is 100% by mass. It is by mass, particularly preferably 3 to 20% by mass.
• Inorganic particles examples include glass powder, ceramic powder, phosphor particles, metal particles and the like.
• glass powder examples include glass powders such as bismuth oxide glass, silicate glass, lead glass, zinc glass, and boron glass, CaO-Al 2 O 3- SiO 2 system, and MgO-Al 2 O 3- SiO.
• glass powders of various silicon oxides such as 2 series, LiO 2- Al 2 O 3- SiO 2 series and the like.
• R is an element selected from the group consisting of Zn, Ba, Ca, Mg, Sr, Sn, Ni, Fe and Mn.
• the ceramic powder examples include alumina, ferrite, zirconia, zircon, barium zirconate, calcium zirconate, titanium oxide, barium titanate, strontium titanate, calcium titanate, magnesium titanate, zinc titanate, and lanthanum titanate. , Neodium titanate, lead zirconite titanate, alumina nitride, silicon nitride, boron nitride, boron carbide, barium titanate, calcium titanate, magnesium silicate, mulite, steatite, cordierite, forsterite and the like.
• ITO ITO, FTO, niobium oxide, vanadium oxide, tungsten oxide, lanthanum strontium manganite, lanthanum strontium cobalt ferrite, yttria-stabilized zirconia, gadolinium-doped ceria, nickel oxide, lanthanum chromite and the like can also be used.
• a blue phosphor substance, a red phosphor substance, a green phosphor substance and the like conventionally known as a fluorescent substance for a display are used.
• the blue phosphor material include MgAl 10 O 17 : Eu system, Y 2 SiO 5 : Ce system, CaWO 4 : Pb system, BaMgAl 14 O 23 : Eu system, BaMgAl 16 O 27 : Eu system, BaMg 2 Al. 14 O 23 : Eu system, BaMg 2 Al 14 O 27 : Eu system, ZnS: (Ag, Cd) system are used.
• red phosphor material examples include Y 2 O 3 : Eu system, Y 2 SiO 5 : Eu system, Y 3 Al 5 O 12 : Eu system, Zn 3 (PO 4 ) 2 : Mn system, YBO 3 : Eu. System, (Y, Gd) BO 3 : Eu system, GdBO 3 : Eu system, ScBO 3 : Eu system, LuBO 3 : Eu system are used.
• green phosphor material include Zn 2 SiO 4 : Mn-based, BaAl 12 O 19 : Mn-based, SrAl 13 O 19 : Mn-based, CaAl 12 O 19 : Mn- based, YBO 3 : Tb-based, BaMgAl 14 O.
• ZnO Zn system
• ZnS (Cu, Al) system
• ZnS Ag system
• Y 2 O 2 S Eu system
• ZnS Zn system
• (Y, Cd) BO 3 Eu system
• BaMgAl 12 O 23 Eu type
• the metal particles include powders made of nickel, palladium, platinum, gold, silver, aluminum, tungsten, alloys thereof, and the like. Further, a metal such as copper or iron, which has good adsorption characteristics with a carboxyl group, an amino group, an amide group and the like and is easily oxidized, can also be preferably used. These metal powders may be used alone or in combination of two or more. Further, in addition to the metal complex, various carbon blacks, carbon nanotubes and the like may be used.
• the inorganic particles may contain lithium.
• the average particle size of the inorganic particles means a volume average particle size calculated from the particle size distribution measured by using a particle size distribution measuring device based on a laser diffraction method. Examples of such a laser diffraction type particle size distribution measuring device include the HORIBA LA-300 series and the HORIBA LA-920 series (all manufactured by HORIBA, Ltd.).
• the positive electrode active material shows a noble potential by comparing the charge / discharge potentials of the two types of compounds.
• a battery having an arbitrary voltage can be configured by using a negative electrode having a low potential.
• the preferable lower limit is 10% by mass and the preferable upper limit is 90% by mass with respect to the total solid content of the slurry.
• the preferable upper limit is 90% by mass with respect to the total solid content of the slurry.
• liquid medium is not particularly limited, but is preferably excellent in coatability, drying property, dispersibility of inorganic particles, etc. when producing a green sheet.
• liquid medium examples include ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, trimethylpentanediol monoisobutyrate, butyl carbitol, and butyl carbitol acetate.
• the preferable lower limit is 50 parts by mass and the preferable upper limit is 250 parts by mass.
• the slurry for forming a green sheet according to the present embodiment may contain a plasticizer, if necessary.
• a plasticizer such as tributyl citrate, dibutyl phthalate, or dibutyl sebacate.
• the preferable lower limit is 0.1% by mass and the preferable upper limit is 3% by mass with respect to the total solid content of the slurry.
• the slurry for green sheet molding according to the present embodiment contains, if necessary, flame-retardant aids, thickeners, defoamers, leveling agents, adhesion-imparting agents, etc. Such additives may be contained.
• the manufacturing method of the slurry for forming a green sheet according to the present embodiment is not particularly limited, and examples thereof include conventionally known methods, in which various mixers such as ball mills, bead mills, blender mills, and three rolls are used for each component. There is a method of mixing using.
• the green sheet according to the embodiment of the present invention is formed by applying and drying the above-mentioned green sheet molding slurry on a base material.
• Specific examples thereof include a method in which the above-mentioned slurry for forming a green sheet is applied onto a support film that has undergone a single-sided mold release treatment, and the liquid medium is dried to form a sheet.
• the support film is preferably a resin film having heat resistance, solvent resistance, and flexibility. Since the support film has flexibility, the slurry can be applied to the surface of the support film by a roll coater, a blade coater, or the like, and the obtained sheet can be stored and supplied in a rolled state. it can.
• the material of the support film examples include fluororesin such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose.
• the thickness of the support film is preferably, for example, 20 ⁇ m to 100 ⁇ m. Further, it is preferable that the surface of the support film is subjected to a mold release treatment. Thereby, the peeling operation of the support film can be easily performed.
• the device according to the embodiment of the present invention is manufactured from the above-mentioned green sheet.
• a multilayer ceramic capacitor can be manufactured by using the above-mentioned green sheet as a dielectric green sheet and further using a conductive paste.
• the conductive paste is a paste-like composition containing a conductive powder, a binder resin, and a liquid medium.
• the material of the conductive powder is not particularly limited as long as it is a conductive material, and examples thereof include nickel, palladium, platinum, gold, silver, copper, and alloys thereof. These conductive powders may be used alone or in combination of two or more.
• the binder resin and the liquid medium are not particularly limited, but the same binder composition for green sheet molding as described above and the slurry for green sheet molding described above can be used. In particular, it is preferable to use the polymer (A) as the binder resin.
• the method for printing the conductive paste is not particularly limited, and examples thereof include a screen printing method, a die coat printing method, an offset printing method, a gravure printing method, and an inkjet printing method.
• an all-solid-state battery can be manufactured by using the above-mentioned green sheet as a material for a positive electrode, a solid electrolyte, and a negative electrode of an all-solid-state battery.
• the all-solid-state battery laminate is composed of a single battery composed of a positive electrode layer, a solid electrolyte layer, and a negative electrode layer.
• a positive electrode layer is arranged on one surface of the solid electrolyte layer, and a negative electrode layer is arranged on the other surface of the solid electrolyte layer.
• the positive electrode layer and the negative electrode layer are provided at positions facing each other via the solid electrolyte.
• the positive electrode layer contains a solid electrolyte and a positive electrode active material
• the negative electrode layer contains a solid electrolyte and a negative electrode active material
• the solid electrolyte layer contains a solid electrolyte.
• At least one of the positive electrode layer and the negative electrode layer contains carbon or the like as a conductive agent.
• a first slurry formed from an electrode active material of either a positive electrode active material or a negative electrode active material and the above-mentioned binder composition for forming a green sheet is formed.
• a molded body and a second molded body formed from a slurry containing a solid electrolyte and the above-mentioned binder composition for forming a green sheet are produced (molded body manufacturing step).
• the binder composition used when producing the first molded product and the binder composition used when producing the second molded product may be the same composition or different compositions. It may be.
• the first molded body and the second molded body are laminated to form a laminated molded body (laminated molded body manufacturing step). Then, the obtained laminated molded body is fired to form a laminated fired body composed of an electrode layer and a solid electrolyte layer (laminated fired body forming step). In this way, a molded product is produced from the slurry, and the molded products of the positive electrode layer, the solid electrolyte layer, and the negative electrode layer are laminated to form a laminated molded product, and the laminated molded product is fired to obtain an all-solid-state battery. Can be manufactured.
• the laminated fired body may be a laminated body having a single battery structure in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated, and a plurality of the laminated bodies having the above single battery structure are interposed with a current collector layer interposed therebetween. It may be a laminated body. In this case, a plurality of laminated bodies having a single battery structure may be electrically stacked in series or in parallel.
• the method for forming the above-mentioned molded product is not particularly limited, but a die coater, a comma coater, screen printing, or the like can be used.
• the method for laminating the molded bodies is not particularly limited, but the molded bodies can be laminated using a hot isotropic press, a cold isotropic press, a hydrostatic press, or the like.
• Example 1 4.1.1. Synthesis of polymer (A) and evaluation of physical properties ⁇ Synthesis of polymer (A)> A uniform solution prepared by mixing 20 parts by mass of 2-methacryloyloxyethyl phthalic acid, 80 parts by mass of 2-ethylhexyl methacrylate, and 2 parts by mass of 2,2′-azobis (2-methylpropionate) dimethyl was prepared with 0.1% polyvinyl. In addition to 900 parts by mass of an aqueous alcohol solution, the mixture was stirred with a homomixer at 500 rpm for 30 minutes.
• This dispersion was placed in a separable flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux condenser, and heated at 70 ° C. for 4 hours under a nitrogen stream for polymerization. After completion of the polymerization, when cooled and left to stand, the reaction system was separated into two layers of a polymer and clear water, and almost no emulsion polymer was observed. This was filtered using a nutche, and the polymer particles were taken out, washed with water and filtered repeatedly, and further dried to obtain 80 parts by mass of the polymer (A). With respect to the obtained polymer (A), the weight average molecular weight (Mw), the glass transition temperature (Tg) and the thermal decomposition residue were measured by the following methods.
• the polymer (A) obtained above was raised from room temperature to 400 ° C. at a heating rate of 10 ° C./min under a nitrogen atmosphere using a differential thermogravimetric simultaneous measurement device "STA7200RV" manufactured by Hitachi High-Technologies Corporation. After warming, the mixture was maintained at 400 ° C. for 1 hour, and the residual rate was calculated from the change in cell weight before and after the test. As a result, the polymer residue was 0.03%.
• a binder composition (1) was prepared by dissolving the polymer (A) obtained above in an isopropanol solvent so that the solid content concentration was 10% by mass. To 44 parts by mass of the binder composition (1) thus obtained, 55 parts by mass of nickel powder as a conductive powder and 1 part by mass of oleic acid as a dispersant were added, mixed by a three-roll mill, and the conductive paste was added.
• the binder composition (2) was prepared by dissolving the polymer (A) obtained above in a butyl acetate solvent so that the solid content concentration was 7.5% by mass. To 67 parts by mass of the binder composition (2) thus obtained, 32 parts by mass of barium titanate (average particle diameter 0.2 ⁇ m) as inorganic particles and 1 part by mass of dibutyl phthalate as a plasticizer were added. , A slurry for forming a green sheet was obtained by mixing using a ball mill. This slurry for forming a green sheet is applied onto a release-treated polyester film so that the thickness after drying is 1 ⁇ m, dried at room temperature for 1 hour, and then dried at 80 ° C. for 3 hours using a hot air dryer. Then, a ceramic green sheet was prepared by drying at 120 ° C. for 2 hours.
• the conductive paste obtained above is applied to one side of the ceramic green sheet obtained above by a screen printing method so that the thickness after drying is 1.5 ⁇ m, and the surface is dried to conduct conductivity. A layer was formed to obtain a conductive layer-forming ceramic green sheet.
• the obtained conductive layer-forming ceramic green sheet was cut into 5 cm squares, 100 sheets were stacked, and heated and pressure-bonded for 10 minutes under the conditions of a temperature of 70 ° C. and a pressure of 150 kg / cm 2, to obtain a laminated body.
• the obtained laminate was heated to 400 ° C. at a heating rate of 3 ° C./min under a nitrogen atmosphere and held for 5 hours, then heated to 1350 ° C. at a heating rate of 5 ° C./min and held for 10 hours. By doing so, a ceramic fired body was produced.
• the solid electrolyte slurry obtained above is coated on a PET film using the doctor blade method, formed into a sheet having a thickness of 30 ⁇ m, and punched into a disk having a diameter of 31 mm to form a solid.
• An electrolyte green sheet was prepared.
• one electrode green sheet peeled from the PET film was laminated on one side of the solid electrolyte layer obtained above, and pressed at a temperature of 60 ° C. for pressure bonding to form a positive electrode layer.
• a negative electrode layer was formed by pressure-bonding two electrode sheets to the opposite surfaces of the solid electrolyte layer in the same manner. In this way, a green sheet laminate for an all-solid-state battery was produced.
• the reason why there is a difference in the number of electrode sheets used in the positive electrode layer and the negative electrode layer is that Li 3 V 2 (PO 4 ) 3 is used as the positive electrode active material and the negative electrode active material. This is because it is taken into consideration that the capacities of Li 3 V 2 (PO 4 ) 3 per unit weight (gram) differ by about twice.
• the thicknesses of the positive electrode layer and the negative electrode layer can be appropriately changed depending on the material of the electrode active material to be used.
• Vacuum packing was performed with an aluminum laminated film to ensure contact between the laminated fired body and the copper foil and the aluminum foil, and an all-solid-state battery was produced.
• Example 2-9 Comparative Examples 1-5
• the binder composition and green sheet are the same as in Example 1 above, except that the polymer having the polymer composition shown in Table 1 below is synthesized in the same manner as in ⁇ Synthesis of Polymer (A)> in Example 1. , And an all-solid-state battery was prepared and evaluated in the same manner as in Example 1 above.
• the binder compositions of Comparative Examples 1 to 3 have high green sheet strength, they have poor polymer thermal decomposability, which adversely affects the battery characteristics. Further, regarding the binder composition of Comparative Example 4, although the thermal decomposability of the polymer was good, the strength of the green sheet was very weak, and the device could not be manufactured. Further, the binder composition of Comparative Example 5 is an example in which the content ratio of the chain transfer agent is changed to 1 part by mass from the composition of Comparative Example 4, but the thermal decomposability of the polymer deteriorates and the green sheet strength is also very high. It turns out that it remains vulnerable to.
• the polymer (A) described in the examples of the present application can be obtained by simple radical polymerization, it is also an advantage that a highly productive polymerization method such as suspension polymerization, solution polymerization, or emulsion polymerization can be adopted.
• the present invention is not limited to the above embodiment, and various modifications are possible.
• the present invention includes substantially the same configurations as those described in the embodiments (eg, configurations with the same function, method and result, or configurations with the same purpose and effect).
• the present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration.
• the present invention also includes a configuration that exhibits the same effects as the configuration described in the above embodiment or a configuration that can achieve the same object.
• the present invention also includes a configuration in which a known technique is added to the configuration described in the above embodiment.

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• 2020
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