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WO2013081077A1 - Pâte conductrice et condensateur céramique multicouche - Google Patents

Pâte conductrice et condensateur céramique multicouche Download PDF

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Publication number
WO2013081077A1
WO2013081077A1 PCT/JP2012/080994 JP2012080994W WO2013081077A1 WO 2013081077 A1 WO2013081077 A1 WO 2013081077A1 JP 2012080994 W JP2012080994 W JP 2012080994W WO 2013081077 A1 WO2013081077 A1 WO 2013081077A1
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WO
WIPO (PCT)
Prior art keywords
conductive paste
group
carbon atoms
paste according
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/080994
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English (en)
Japanese (ja)
Inventor
徳地　一記
真輔 新居
悠太 田岡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
Original Assignee
Kuraray Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2011259864A external-priority patent/JP2013114890A/ja
Priority claimed from JP2011259865A external-priority patent/JP2013114891A/ja
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Priority to KR1020147015591A priority Critical patent/KR20140106548A/ko
Priority to CN201280058409.8A priority patent/CN103946926A/zh
Publication of WO2013081077A1 publication Critical patent/WO2013081077A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • C04B35/465—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 based on alkaline earth metal titanates
    • C04B35/468—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 based on alkaline earth metal titanates based on barium titanates
    • C04B35/4682—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 based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
    • 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
    • C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • 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
    • H01G4/005—Electrodes
    • H01G4/008—Selection of materials
    • 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
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/34—Oxidic
    • C04B2237/345—Refractory metal oxides
    • C04B2237/346—Titania or titanates

Definitions

  • the present invention relates to a conductive paste used for forming an internal electrode layer of a multilayer electronic component such as a multilayer ceramic capacitor or a conductive layer of a solar cell, and a multilayer ceramic capacitor obtained using the conductive paste and a ceramic green sheet. About.
  • a multilayer ceramic capacitor is a chip-type ceramic capacitor in which a large number of dielectric layers such as titanium oxide and barium titanate and internal electrode layers are stacked.
  • Such a multilayer ceramic capacitor is manufactured by the following method, for example. First, in an organic solvent in which ceramic powder is dispersed, a binder resin such as polyvinyl butyral resin and a plasticizer are added, and a slurry composition for a ceramic green sheet is prepared by uniformly mixing with a ball mill or the like. The slurry composition is cast-molded on a releasable support such as a polyethylene terephthalate film, the solvent is removed by heating or the like, and then peeled from the support to produce a ceramic green sheet.
  • a binder resin such as polyvinyl butyral resin and a plasticizer
  • the ceramic green sheet obtained in this way is used after being peeled off from the peelable support.
  • a plurality of laminates obtained by alternately applying a conductive paste serving as an internal electrode on the surface of a ceramic green sheet by screen printing or the like are heated and pressed to obtain a laminate.
  • a laminated body is formed by various processes and cut into a predetermined shape. Then, through a process of thermally decomposing and removing the binder component contained in the laminate, so-called degreasing treatment, and then sintering the external electrode on the end face of the ceramic fired product obtained by firing.
  • a multilayer ceramic capacitor can be manufactured.
  • ceramic green sheets have been made thinner and multilayered for the purpose of reducing the size and increasing the capacity of multilayer ceramic capacitors.
  • the difference between the part where the conductive paste is printed and the part where the conductive paste is not printed becomes larger.
  • the deformation of the sheet and the internal electrode layer has occurred, resulting in a problem that the electrical characteristics and reliability of the multilayer ceramic capacitor are lowered.
  • printability is insufficient with conventional conductive pastes.
  • Patent Document 1 a conductive paste containing a specific modified polyvinyl acetal resin has been proposed (see Patent Document 1).
  • Patent Document 1 when printing the conductive paste on the ceramic green sheet, the binder such as polyvinyl butyral resin in the ceramic green sheet is dissolved by the organic solvent contained in the conductive paste, so that the sheet attack resistance is not good. It was enough. Further, the thixotropic property of the conductive paste was insufficient.
  • the thixotropic property of the conductive paste means a property in which the apparent viscosity is low when the shear rate is high, and the apparent viscosity is high when the shear rate is low and when the shear rate is not sheared.
  • Patent Document 2 aqueous slurry containing a polyvinyl alcohol polymer (hereinafter sometimes abbreviated as “PVA”) is used instead of an organic slurry as a slurry composition for a ceramic green sheet.
  • PVA polyvinyl alcohol polymer
  • Patent Document 2 does not describe the use of an aqueous solvent as a solvent for a conductive paste printed on a ceramic green sheet, and the thixotropy and sheet attack resistance of the conductive paste are still insufficient. .
  • An object of the present invention is to provide a conductive paste that is excellent in printability such as thixotropy, as well as stringing resistance, bleeding resistance, and sheet attack resistance. Furthermore, it aims at providing the electrically conductive paste which can manufacture a laminated ceramic capacitor efficiently.
  • the viscosity average polymerization degree of the coalescence is 200 or more and 5,000 or less
  • the saponification degree is 20 mol% or more and 99.99 mol% or less
  • the content of the monomer unit (A) is 0.05 mol% or more.
  • R 2 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • M and n are the number of repeating units of oxyalkylene units, respectively.
  • M is an integer of 1 to 30, and n is an integer of 1 to 20.
  • “b” indicates that both adjacent units are formed by block copolymerization.)
  • the conductive paste of the present invention is excellent in printability such as thixotropy, yarn pulling resistance, bleeding resistance and sheet attack resistance. Therefore, the conductive paste of the present invention can be suitably used as a conductive paste used for forming an internal electrode layer of a multilayer electronic component such as a multilayer ceramic capacitor or a conductive layer of a solar cell.
  • the multilayer ceramic capacitor of the present invention is less susceptible to deformation, delamination, etc. of the ceramic green sheet and internal electrode layer, and is excellent in electrical characteristics, reliability, and the like.
  • the above-mentioned thread pulling resistance or bleeding resistance means that stringing or bleeding is less likely to occur.
  • the stringing means that the conductive paste does not peel off cleanly from the plate used for printing, and the printing surface is in a state where the thread is pulled. This means that the apparent viscosity of the conductive paste is high in a state where the shear rate is high. Occurs when.
  • blotting refers to a phenomenon in which a printed conductive paste flows on a ceramic green sheet and is printed in a state where it is wider than a target printed shape. This is a state in which the shear rate is low and unsheared. Occurs when the apparent viscosity of the conductive paste is low.
  • the electrically conductive paste of this invention contains specific modified PVA, electrically conductive powder, and an aqueous solvent, and may contain another component as needed. Hereinafter, each component contained in the electrically conductive paste of this invention is demonstrated.
  • the modified PVA used in the present invention contains a monomer unit (A) having a group having 5 or more carbon atoms.
  • A monomer unit
  • the group having 5 or more carbon atoms is an alkyl group having 5 to 29 carbon atoms or a polyoxyalkylene group, that is, the modified PVA is an alkyl-modified PVA, polyoxyalkylene-modified PVA (hereinafter referred to as “polyoxyalkylene”). Is sometimes abbreviated as “POA”).
  • the alkyl-modified PVA used in the present invention preferably contains a monomer unit having an alkyl group having 5 to 29 carbon atoms. That is, the alkyl-modified PVA is preferably a copolymer containing the monomer unit having an alkyl group having 5 to 29 carbon atoms and a vinyl alcohol unit (—CH 2 —CHOH—). Furthermore, other monomer units may be contained. When such an alkyl-modified PVA is used, the thixotropic property of the obtained conductive paste is improved by the hydrophobic group interaction in the alkyl-modified PVA.
  • the printed portion is difficult to spread, and printability such as stringing resistance and bleeding resistance is improved.
  • the number of carbon atoms of the alkyl group is less than 5, the interaction between the alkyl groups is not sufficiently exhibited, so that the thixotropic property is lowered.
  • the carbon number of the alkyl group exceeds 29, the water solubility and handling property at high temperature of the alkyl-modified PVA are lowered.
  • an alkyl group having 8 to 29 carbon atoms is more preferable, an alkyl group having 12 to 27 carbon atoms is more preferable, and an alkyl group having 15 to 26 carbon atoms is more preferable. Particularly preferred is an alkyl group having 17 to 24 carbon atoms.
  • Examples of the monomer unit having an alkyl group having 5 to 29 carbon atoms include monomer units derived from ⁇ -olefins such as 1-octene and 1-decene; pentyl vinyl ether, octyl vinyl ether, nonyl vinyl ether, dodecyl Monomer units derived from vinyl ethers such as vinyl ether and octadecyl vinyl ether; alkyl (meth) acrylates; N-alkyl (meth) acrylamide units represented by the following formula (II) are preferred, and R 3 below has 8 or more carbon atoms. N-alkyl (meth) acrylamide units that are 29 or less alkyl groups are more preferred.
  • R 3 represents a linear or branched alkyl group having 5 to 29 carbon atoms.
  • R 4 represents a hydrogen atom or a methyl group.
  • R 3 and R 4 may have a substituent such as a halogen atom as long as the effects of the present invention are not impaired, but preferably do not have these substituents. .
  • Examples of the alkyl group having 5 to 29 carbon atoms represented by R 3 include a pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, pentadecyl group, and nonadecyl group. It is done. Among these, from the viewpoint of further improving thixotropy, an alkyl group having 8 to 29 carbon atoms is preferable, an alkyl group having 12 to 27 carbon atoms is more preferable, and an alkyl group having 15 to 26 carbon atoms is further included. An alkyl group having 17 to 24 carbon atoms is particularly preferable.
  • R 4 is a hydrogen atom or a methyl group from the viewpoint of ease of synthesis and the like.
  • the POA-modified PVA used in the present invention has a POA group in the side chain.
  • the POA group is preferably a POA group having an alkylene group having 1 to 8 carbon atoms, and at least one POA selected from the group consisting of a polyoxyethylene group, a polyoxypropylene group and a polyoxybutylene group. More preferably, it is a group.
  • the POA-modified PVA in the conductive paste functions as a binder.
  • the two or more oxyalkylene groups may be either random or block.
  • the block shape is preferable from the viewpoint of easily expressing the physical properties based on the POA group.
  • the number of oxyalkylene units in the oxyalkylene group in the POA group is preferably 2 or more, 50 or less, more preferably 5 or more and 40 or less, further preferably 8 or more and 30 or less, and more preferably 10 or more and 25 or less. It is particularly preferred. Thus, when the number of oxyalkylene units of the oxyalkylene group is in the above range, the thixotropic property of the obtained conductive paste is further improved.
  • the said POA group consists of 2 or more types of oxyalkylene groups, let the total number of oxyalkylene units of each oxyalkylene group be the number of oxyalkylene units of an oxyalkylene group.
  • the number of units means a weighted average of the total number of oxyalkylene units of the oxyalkylene group of each POA group.
  • the POA group is particularly preferably a POA group represented by the above formula (I).
  • R 1 is a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of productivity.
  • R 2 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • R 2 is preferably a hydrogen atom, a methyl group or a butyl group, more preferably a hydrogen atom or a methyl group.
  • m and n each represent the average number of repeating units of the oxyalkylene group, m is an integer of 1 to 30, and n is an integer of 1 to 20.
  • a unit having the number of repeating units m is referred to as unit 1
  • a unit having the number of repeating units n is referred to as unit 2.
  • the number of repeating units m of the unit 1 of the POA group represented by the above formula (I) is an integer of 1 to 30, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and an integer of 1 to 5 Further preferred.
  • the number m of repeating units is in the above range, the thixotropy of the obtained conductive paste is further improved.
  • the number of repeating units n of the POA group unit 2 represented by the above formula (I) is an integer of 1 to 20, preferably an integer of 5 to 18, and more preferably an integer of 8 to 15.
  • the number of repeating units n is in the above range, the thixotropic property of the obtained conductive paste is further improved.
  • the method for producing the alkyl-modified PVA is not particularly limited, but the unsaturated monomer represented by the following formula (III) and a vinyl ester monomer are copolymerized. A method of saponifying the resulting alkyl-modified vinyl ester polymer is preferred.
  • Examples of the unsaturated monomer represented by the above formula (III) include N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide, N-octadecylacrylamide, N-hexacosylacrylamide, and N-octylmethacrylamide.
  • N-octadecyl acrylamide, N-octyl methacrylamide, N-decyl methacrylamide, N-dodecyl methacrylamide, N-octadecyl methacrylamide, N-hexacosyl methacrylamide are preferred, and N-octadecyl acrylamide, N- Dodecyl methacrylamide and N-octadecyl methacrylamide are more preferable, and N-octadecyl acrylamide and N-octadecyl methacrylamide are more preferable.
  • the production method of the POA-modified PVA is not particularly limited, but copolymerization of an unsaturated monomer having a POA group in the side chain and a vinyl ester monomer is performed, A method of saponifying the obtained POA-modified vinyl ester polymer is preferred.
  • an unsaturated monomer having a POA group represented by the above formula (I) in the side chain is preferable, and an unsaturated monomer represented by the following formula (IV): It is preferable that it is a body. That is, the POA-modified vinyl ester system obtained by copolymerizing an unsaturated monomer represented by the following formula (IV) having a POA group represented by the above formula (I) and a vinyl ester monomer. A method of saponifying the polymer is more preferable.
  • R 1 , R 2 , m and n are the same as those in the above formula (I).
  • R 5 represents a hydrogen atom or a COOM group, where M represents a hydrogen atom, an alkali metal or an ammonium group.
  • R 6 represents a hydrogen atom, a methyl group or a CH 2 —COOM group, where M is as defined above.
  • X represents —O—, —CH 2 —O—, —CO—, — (CH 2 ) k—, —COO—, —CO—NR 7 — or CO—NR 7 —CH 2 —.
  • R 7 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • k is an integer of 1 to 15.
  • R 1 , R 2 , m and n are the same as those described above in the description of the formula (I).
  • R 5 is preferably a hydrogen atom
  • R 6 is preferably a hydrogen atom or a methyl group.
  • X -CH 2 -O -, - CO -NR 7 - or CO-NR 7 -CH 2 - is - it is preferably, -CO-NR 7 - or CO-NR 7 -CH 2 It is more preferable.
  • R 7 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
  • the unsaturated monomer represented by the above formula (IV) is polyoxyalkylene.
  • examples include mono (meth) acrylic acid amide, polyoxyalkylene mono (meth) allyl ether, polyoxyalkylene monovinyl ether, and polyoxyalkylene mono (meth) acrylate.
  • polyoxyethylene polyoxybutylene monoacrylic acid Amide N-methylene polyoxyethylene polyoxybutylene monoacrylic amide, Polyoxyethylene polyoxybutylene monomethacrylamide, N-methylene polyoxyethylene polyoxybutylene monomethacrylamide, Polyoxyethylene polyoxybutylene monoallyl ether , Poly Xylethylene polyoxybutylene monomethallyl ether, polyoxyethylene polyoxybutylene monovinyl ether, polyoxyethylene polyoxybutylene monoacrylate, polyoxyethylene polyoxybutylene monomethacrylate, polyoxypropylene polyoxybutylene monoacrylic amide, N- Methylene polyoxypropylene polyoxybutylene monoacrylic amide, polyoxypropylene polyoxybutylene monomethacrylamide, N-methylene polyoxypropylene polyoxybutylene monomethacrylamide, polyoxypropylene polyoxybutylene monoallyl ether, polyoxypropylene Polyoxybutylene monomethallyl ether, polyoxypropylene Polyoxybuty
  • polyoxyethylene polyoxybutylene monoacrylic amide, N-methylene polyoxyethylene polyoxybutylene monoacrylic amide, polyoxyethylene polyoxybutylene monomethacrylamide, N-methylene polyoxyethylene polyoxybutylene mono Methacrylic acid amide, polyoxyethylene polyoxybutylene monoallyl ether are preferably used, and polyoxyethylene polyoxybutylene monomethacrylic acid amide, N-methylene polyoxyethylene polyoxybutylene monomethacrylic acid amide, polyoxyethylene polyoxybutylene Monoallyl ether is more preferably used, and polyoxyethylene polyoxybutylene monomethacrylamide, N-methylene polyoxyethylene polyoxybutylene Methacrylamide are more preferred.
  • R 2 in the above formula (IV) is an alkyl group having 1 to 8 carbon atoms
  • R 5 is a hydrogen atom
  • R 6 is a hydrogen atom or a methyl group
  • the unsaturated monomer represented by the above formula (IV) Specific examples include those in which the terminal hydroxyl group of the above unsaturated monomer exemplified when R 2 in the above formula (IV) is a hydrogen atom is substituted with an alkoxy group having 1 to 8 carbon atoms.
  • Saturated monomers are preferably used, and unsaturated monomers in which the hydroxyl group at the terminal of polyoxyethylene polyoxybutylene monomethacrylamide, N-methylene polyoxyethylene polyoxybutylene monomethacrylamide is substituted with a methoxy group Is particularly preferably used.
  • the temperature at which the unsaturated monomer represented by the above formula (III) or the above formula (IV) is copolymerized with the vinyl ester monomer is not particularly limited, but is preferably 0 ° C. or higher and 200 ° C. or lower, 30 degreeC or more and 140 degrees C or less are more preferable.
  • the copolymerization temperature is lower than 0 ° C., it is difficult to obtain a sufficient polymerization rate.
  • polymerization is higher than 200 degreeC, the modified PVA which has the content rate (henceforth "content rate S") of the monomer unit (A) prescribed
  • the heat generated by the polymerization is balanced with the heat released from the surface of the reactor.
  • Examples thereof include a method and a method of controlling by an external jacket using an appropriate heat medium, but the latter method is preferable from the viewpoint of safety.
  • a polymerization method employed for carrying out the copolymerization of the unsaturated monomer represented by the above formula (III) or the above formula (IV) and the vinyl ester monomer batch polymerization, semi-batch polymerization, continuous Either polymerization or semi-continuous polymerization may be used.
  • the polymerization method an arbitrary method can be adopted from known methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method.
  • a bulk polymerization method or a solution polymerization method in which polymerization is performed in the absence of a solvent or in the presence of an alcohol solvent is preferably employed.
  • an emulsion polymerization method is employed.
  • the alcohol solvent used in the bulk polymerization method or the solution polymerization method methanol, ethanol, n-propanol or the like can be used, but is not limited thereto. Two or more kinds of these solvents can be used in combination.
  • azo initiators As the initiator used for copolymerization, conventionally known azo initiators, peroxide initiators, redox initiators and the like are appropriately selected according to the polymerization method.
  • the azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4- Dimethyl valeronitrile) and the like
  • peroxide initiators include perisopropyl compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; t-butyl Perester compounds such as peroxyneodecanate, ⁇ -cumylperoxyneodecanate, and t-butylperoxydecanate; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethyl
  • the initiator can be combined with potassium persulfate, ammonium persulfate, hydrogen peroxide, or the like to form an initiator.
  • the redox initiator include a combination of the above-described peroxide and a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, Rongalite and the like.
  • the unsaturated monomer represented by the above formula (III) or the above formula (IV) and the vinyl ester monomer when copolymerization of the unsaturated monomer represented by the above formula (III) or the above formula (IV) and the vinyl ester monomer is performed at a high temperature, it is caused by decomposition of the vinyl ester monomer.
  • the PVA may be colored.
  • an antioxidant such as tartaric acid may be added to the polymerization system in an amount of 1 ppm to 100 ppm (with respect to the mass of the vinyl ester monomer) for the purpose of preventing coloring.
  • Vinyl ester monomers used for copolymerization include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, and lauric acid. Examples thereof include vinyl, vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate and the like. Of these, vinyl acetate is most preferred.
  • Acrylic acid esters such as n-butyl acrylate, i-butyl acrylate, t-butyl acrylate; methacrylic acid and its salts; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-methacrylic acid i- Methacrylic acid esters such as propyl, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, ru; acrylamide; N-methyl acrylamide, N-ethyl acrylamide, N, N-dimethyl acrylamide, diacetone acrylamide Acrylamide propanesulfur Acryl acid and its salts, Acrylamidepropyldimethylamine and its salts or quaternary salts thereof, Acrylamide derivatives such as N-methylolacrylamide and its derivatives; Methacrylamide; N-Methylmethacrylamide, N-ethylmeth
  • the degree of polymerization of the resulting modified vinyl ester polymer is adjusted. Therefore, the copolymerization may be carried out in the presence of a chain transfer agent within the range not impairing the gist of the present invention.
  • Chain transfer agents include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; halogenated hydrocarbons such as trichloroethylene and perchloroethylene; sodium phosphinate 1 And phosphinic acid salts such as hydrates.
  • aldehydes and ketones are preferably used. What is necessary is just to determine the addition amount of a chain transfer agent according to the chain transfer constant of the chain transfer agent to add, and the polymerization degree of the target vinyl ester polymer. Generally, the content is preferably 0.1% by mass or more and 10% by mass or less based on the vinyl ester monomer.
  • a conventional alcoholic acid decomposition reaction or hydrolysis using a basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methoxide or an acidic catalyst such as p-toluenesulfonic acid can be applied.
  • the solvent that can be used in this reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and toluene. These can be used alone or in combination of two or more. Among them, it is convenient and preferable to perform the saponification reaction using methanol or a methanol / methyl acetate mixed solution as a solvent and sodium hydroxide as a catalyst.
  • the content S of the monomer unit (A) having a group having 5 or more carbon atoms needs to be 0.05 mol% or more and 5 mol% or less, and 0.1 mol%
  • the content is preferably 2 mol% or less and more preferably 0.2 mol% or more and 1 mol% or less.
  • the content S of the monomer unit (A) in the present specification is the ratio of the number of moles of the monomer unit having a group having 5 or more carbon atoms in the number of moles of all structural units constituting the modified PVA. is there.
  • the modified PVA When the content S exceeds 5 mol%, the ratio of the modifying group contained per molecule of the modified PVA increases, and the water solubility of the modified PVA decreases. On the other hand, when the content S is less than 0.05 mol%, the modified PVA has excellent water solubility, but the modified PVA contains a small number of groups having 5 or more carbon atoms, and is a conductive paste based on modification. The thixotropy, yarn pulling resistance and bleeding resistance are not fully expressed.
  • the content S may be obtained from the modified PVA or may be obtained from a modified vinyl ester polymer that is a precursor thereof, and both can be obtained from proton NMR.
  • a modified vinyl ester polymer specifically, the reprecipitation purification of the modified vinyl ester polymer is sufficiently performed three times or more with n-hexane / acetone, and then dried under reduced pressure at 50 ° C. For 2 days to prepare a sample for analysis. This sample is dissolved in CDCl 3 and measured at room temperature using proton NMR.
  • the modified PVA is an alkyl-modified PVA
  • R 3 is linear
  • R 4 is a hydrogen atom
  • the peak ⁇ (4.7 to 5.2 ppm) derived from the proton of the main chain methine of the vinyl ester monomer unit and the proton of the terminal methyl group of the unit 2
  • the POA group modification rate S can be calculated from the derived peak ⁇ (0.8 to 1.0 ppm) using the following formula.
  • n represents the number of repeating units of unit 2.
  • POA group modification rate S (mol%) ⁇ ( ⁇ peak area / 3n) / ( ⁇ peak area + ( ⁇ peak area / 3n)) ⁇ ⁇ 100
  • the above-mentioned modified PVA has a viscosity average degree of polymerization (hereinafter also referred to as “viscosity average degree of polymerization P”.
  • the viscosity average degree of polymerization is also simply referred to as a degree of polymerization) and needs to be 200 to 5,000, 500 or more and 4,000 or less are preferable, and 1,000 or more and 3,000 or less are more preferable.
  • the degree of polymerization of the modified PVA exceeds 5,000, the productivity of the modified PVA is lowered, which is not practical.
  • the degree of polymerization of the modified PVA is less than 200, the thixotropic property of the obtained conductive paste is not sufficiently developed.
  • the saponification degree of the modified PVA needs to be 20 mol% or more and 99.99 mol% or less, preferably 40 mol% or more and 99.9 mol% or less, more preferably 60 mol% or more and 99.5 mol%, 80 mol% or more and 99 mol% are more preferable.
  • the degree of saponification of the modified PVA is less than 20 mol%, it is difficult to prepare a conductive paste because the water solubility of the modified PVA decreases.
  • the degree of saponification of the modified PVA exceeds 99.99 mol%, production of the modified PVA becomes difficult, which is not practical.
  • the saponification degree of the modified PVA is a value that can be measured according to JIS-K6726.
  • the content ratio of the modified PVA in the conductive paste of the present invention is preferably 0.1% by mass or more and 10% by mass or less from the viewpoint of further improving the thixotropy of the obtained conductive paste.
  • the conductive powder used in the present invention is not particularly limited as long as it exhibits conductivity, and examples thereof include nickel, palladium, platinum, gold, silver, copper, and powders made of these alloys.
  • a conductive powder having an insoluble inorganic oxide, which is an oxide containing silicon, aluminum, or zirconium, adsorbed on the surface is preferably used.
  • the conductive powder is stably dispersed at a high concentration in the aqueous slurry without being re-agglomerated, so that it can be suitably used as a conductive paste for firing, particularly a conductive paste for forming a multilayer ceramic capacitor.
  • the said electrically conductive powder may be used independently, or may use 2 or more types together.
  • the content ratio of the conductive powder in the conductive paste of the present invention is preferably 30% by mass or more and 80% by mass or less from the viewpoint of further improving the thixotropic property of the conductive paste obtained.
  • aqueous solvent In the conductive paste of the present invention, it is important to use an aqueous solvent as a solvent. The reason is that the modified PVA has a high polarity because it has a large number of hydroxyl groups in the molecule, and tends to be hardly dissolved in an organic solvent. Therefore, the conductive paste of the present invention can be easily produced by using an aqueous solvent.
  • the aqueous solvent is not particularly limited, but from the viewpoints of safety to human body, environmental pollution, possibility of fire, possibility of explosion, etc., those mainly composed of water are preferable.
  • the content of water is more preferably 60% by mass or more, further preferably 70% by mass or more, particularly preferably 80% by mass or more, and may be 100% by mass.
  • the water is preferably distilled water or ion exchange water, and more preferably ion exchange water.
  • the content ratio of the aqueous solvent in the conductive paste of the present invention is preferably 20% by mass or more and 70% by mass or less from the viewpoint of further improving the thixotropic property of the conductive paste obtained.
  • the conductive paste of the present invention is a water-soluble polymer such as various known PVAs (excluding the modified PVA used in the present invention), starch, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, and the like, as long as the gist of the present invention is not impaired.
  • Other components such as an agent, a lubricant, a dispersant, and an antistatic agent may be contained.
  • the method for producing the conductive paste of the present invention is not particularly limited.
  • the conductive powder, the modified PVA, the aqueous solvent and other components are supplied to a known mixer such as a blender mill, three rolls, and kneaded.
  • the manufacturing method of the electrically conductive paste to do can be employ
  • the viscosity of the conductive paste of the present invention is not particularly limited, but the viscosity ratio ⁇ 2 / ⁇ between the viscosity ⁇ 1 at a shear rate of 1 (1 / sec) and the viscosity ⁇ 2 at a shear rate of 100 (1 / sec). 1 is preferably 0.8 or less, more preferably 0.5 or less, further preferably 0.3 or less, and particularly preferably 0.1 or less. It is preferable that the viscosity ratio ⁇ 2 / ⁇ 1 is in the above range since the thixotropy can be further enhanced and a conductive paste that is more excellent in string resistance and bleed resistance can be obtained.
  • the electrically conductive paste of this invention is used suitably for formation of the internal electrode layer of multilayer type electronic components, such as a multilayer ceramic capacitor, and formation of the conductive layer of a solar cell. Therefore, a multilayer ceramic capacitor obtained using the conductive paste and ceramic green sheet of the present invention is also one aspect of the present invention. Since the conductive paste of the present invention has excellent printability such as thixotropy, string resistance, bleed resistance, and sheet attack resistance, a multilayer ceramic capacitor can be efficiently produced by using the conductive paste.
  • the method for producing the slurry composition used for the ceramic green sheet is not particularly limited.
  • a binder resin such as polyvinyl acetal resin, ceramic powder, an organic solvent, and various additives to be added as necessary are ball mill, blender
  • the method for producing the ceramic green sheet is not particularly limited and can be produced by a conventionally known production method.
  • the ceramic green sheet slurry composition is cast on a peelable support such as a polyethylene terephthalate film.
  • a method of forming and removing the solvent by heating or the like and then peeling off from the support is employed.
  • a multilayer ceramic capacitor can be produced by laminating a ceramic green sheet obtained in this manner with a printed (coated) conductive paste of the present invention.
  • a plurality of sheets obtained by applying the conductive paste of the present invention to the surface of the ceramic green sheet by screen printing or the like are alternately stacked and heat-pressed to form a laminate, and the resin contained in the laminate
  • a method of sintering an external electrode on the end face of the ceramic fired product obtained by pyrolyzing and removing (degreasing treatment) and the like is employed.
  • the multilayer ceramic capacitor of the present invention can be obtained by laminating a ceramic green sheet obtained by printing (coating) the conductive paste. Therefore, the multilayer ceramic capacitor is excellent in electrical characteristics, reliability, and the like, unlikely to cause deformation and delamination of the ceramic green sheet and internal electrode layers.
  • the PVA (alkyl-modified PVA, POA-modified PVA and unmodified PVA) obtained by the following production examples was evaluated according to the following method.
  • Viscosity average polymerization degree P and degree of saponification of PVA The viscosity average polymerization degree P and saponification degree of PVA were determined by the method described in JIS-K6726.
  • the temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization.
  • AIBN 2,2′-azobisisobutyronitrile
  • the delay solution was added dropwise to the reactor so that the monomer composition in the polymerization solution was constant, and polymerization was performed at 60 ° C. for 3 hours, followed by cooling to stop the polymerization.
  • the total amount of comonomer added until the polymerization was stopped was 4.8 g.
  • the solid content concentration when the polymerization was stopped was 29.9%. Subsequently, unreacted vinyl acetate monomer was removed while occasionally adding methanol under reduced pressure at 30 ° C.
  • alkyl-modified PVAc an alkyl-modified vinyl acetate polymer
  • alkyl-modified PVAc methanol solution prepared by adding methanol (200.0 g of alkyl-modified PVAc in the solution) was added to 27.9 g of an alkali solution (sodium hydroxide in 10% methanol). Saponification was carried out by addition (concentration of alkyl-modified PVAc in the saponification solution was 25%, and the molar ratio of sodium hydroxide to vinyl acetate units in the alkyl-modified PVAc was 0.03). A gel was formed about 1 minute after the addition of the alkaline solution.
  • the gel-like material was pulverized with a pulverizer and allowed to stand at 40 ° C. for 1 hour to allow saponification to proceed. Then, 500 g of methyl acetate was added to neutralize the remaining alkali. After confirming the completion of neutralization using a phenolphthalein indicator, the mixture was filtered to obtain a white solid. To this white solid, 2,000 g of methanol was added, and the mixture was left to wash at room temperature for 3 hours. This washing operation was repeated three times, and then the white solid obtained by centrifugal drainage was left in a dryer at 65 ° C. for 2 days to obtain alkyl-modified PVA (PVA1).
  • PVA1 had a viscosity average polymerization degree P of 1,700, a saponification degree of 98.5 mol%, and an alkyl modification rate S of 0.4 mol%.
  • the temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization. While the delay solution was added dropwise so that the monomer composition (ratio of vinyl acetate and monomer A) in the polymerization solution was constant, polymerization was performed at 60 ° C. for 3 hours and then cooled to stop the polymerization. The total amount of monomer A added until the polymerization was stopped was 17.6 g. The solid content concentration when the polymerization was stopped was 24.4%. Subsequently, unreacted vinyl acetate monomer was removed while occasionally adding methanol at 30 ° C.
  • AIBN 2,2′-azobisisobutyronitrile
  • POA-modified vinyl ester polymer POA-modified PVAc
  • an alkali solution 10% methanol solution of sodium hydroxide
  • Saponification was carried out (POA modified PVAc concentration of saponified solution 20%, molar ratio of sodium hydroxide to vinyl acetate unit in POA modified PVAc 0.1).
  • a gel-like product was formed in about 1 minute after the addition of the alkaline solution.
  • Example 1 Manufacture of conductive paste
  • 2 g of PVA1 obtained in Production Example 1 and 98 g of ion-exchanged water were supplied to a separable flask equipped with a stirring blade, stirred for 2 hours while heating in a 90 ° C. water bath, and 2% PVA1 An aqueous solution of was prepared.
  • the total amount of the prepared 2% PVA1 aqueous solution and 100 g of nickel powder (Mitsui Metal Mining; 2020SS) as a conductive powder were supplied to three rolls to prepare a conductive paste.
  • Example 2 The conductive paste produced in Example 1 was evaluated by the following method. The evaluation results are shown in Table 2.
  • the obtained ceramic slurry composition was applied onto a release-treated polyester film so that the thickness after drying was about 1 ⁇ m, air-dried at room temperature for 1 hour, a hot-air dryer at 80 ° C. for 3 hours, and then After being dried at 120 ° C. for 2 hours, a ceramic green sheet was produced by peeling off from the polyester film.
  • Viscosity As an index of thixotropy of the conductive paste produced in Example 1, the viscosity of the conductive paste was measured in the FLOW SWEEP mode under the following measurement conditions using a rotary rheometer (manufactured by TA INSTRUMENT; ARES G2). The viscosity at shear rate: 1 (1 / sec) and the viscosity at shear rate: 100 (1 / sec) were measured. The viscosity ⁇ 1 at a shear rate of 1 (1 / sec) is 25 Pa ⁇ s, the viscosity ⁇ 2 at a shear rate of 100 (1 / sec) is 1.5 Pa ⁇ s, and the viscosity ratio ⁇ 2 / ⁇ 1 was 0.06.
  • Example 2 Yarn pulling resistance
  • the conductive paste produced in Example 1 was printed on the ceramic green sheet with a screen printer, and then dried in an oven at 100 ° C. for 30 minutes. Thereafter, the stringiness of the printed portion was observed with an optical microscope and evaluated according to the following criteria.
  • Example 3 Smear resistance
  • the conductive paste produced in Example 1 was printed on the ceramic green sheet with a screen printer, and then dried in an oven at 100 ° C. for 30 minutes. Thereafter, the bleeding resistance of the printed portion was observed with an optical microscope and evaluated according to the following criteria.
  • ⁇ The amount of bleeding is less than 20 ⁇ m.
  • X The amount of bleeding is 20 ⁇ m or more.
  • Example 2 (4) Sheet Attack Resistance After the conductive paste produced in Example 1 was printed on the ceramic green sheet with a screen printer, it was dried in an oven at 100 ° C. for 30 minutes. Thereafter, the sheet attack property of the ceramic green sheet with respect to the conductive paste was evaluated by observing swelling and distortion of the back side of the printed sheet with a stereomicroscope and according to the following criteria. ⁇ : Almost no swelling or distortion. X: There exists swelling and distortion.
  • Example 2 A conductive paste was produced in the same manner as in Example 1 except that PVA2 was used instead of PVA1. About the obtained electrically conductive paste, the viscosity, the string pulling resistance, the bleeding resistance and the sheet attack resistance were evaluated by the same method as in Example 1. The evaluation results are shown in Table 2.
  • Example 3 A conductive paste was produced in the same manner as in Example 1 except that PVA3 was used instead of PVA1. About the obtained electrically conductive paste, the viscosity, the string pulling resistance, the bleeding resistance and the sheet attack resistance were evaluated by the same method as in Example 1. The evaluation results are shown in Table 2.
  • Example 1 A conductive paste was produced in the same manner as in Example 1 except that PVA4 was used instead of PVA1. About the obtained electrically conductive paste, the viscosity, the string pulling resistance, the bleeding resistance and the sheet attack resistance were evaluated by the same method as in Example 1. The evaluation results are shown in Table 2.
  • Example 4 4 g of PVA5 obtained in Production Example 5 and 96 g of ion-exchanged water were supplied to a separable flask equipped with a stirring blade, stirred for 2 hours while heating in a 90 ° C. water bath, and 4% PVA5 An aqueous solution of was prepared. Next, the total amount of the prepared 4% PVA5 aqueous solution and 100 g of nickel powder (Mitsui Metal Mining; 2020SS) as a conductive powder were supplied to three rolls to prepare a conductive paste. About the obtained electrically conductive paste, the viscosity, the string pulling resistance, the bleeding resistance and the sheet attack resistance were evaluated by the same method as in Example 1. The evaluation results are shown in Table 2.
  • Example 5 A conductive paste was produced in the same manner as in Example 4 except that PVA6 was used instead of PVA5. About the obtained electrically conductive paste, the viscosity, the string pulling resistance, the bleeding resistance and the sheet attack resistance were evaluated by the same method as in Example 1. The evaluation results are shown in Table 2.
  • the conductive paste of the present invention is excellent in printability such as thixotropy, yarn pulling resistance, bleeding resistance and sheet attack resistance. Therefore, the conductive paste of the present invention can be suitably used as a conductive paste used for forming an internal electrode layer of a multilayer electronic component such as a multilayer ceramic capacitor or a conductive layer of a solar cell.
  • the multilayer ceramic capacitor of the present invention is less susceptible to deformation, delamination, etc. of the ceramic green sheet and internal electrode layer, and is excellent in electrical characteristics, reliability, and the like.

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Abstract

La présente invention porte sur une pâte conductrice qui a une excellente thixotropie et une excellente aptitude à l'impression telle qu'une résistance au caractère filandreux, une résistance à l'exsudation et une résistance à l'attaque des feuilles. La présente invention porte également sur une pâte conductrice qui permet une fabrication efficace d'un condensateur céramique multicouche. La présente invention concerne une pâte conductrice qui contient : un polymère d'alcool polyvinylique modifié qui contient une unité monomère (A) ayant un groupe ayant au moins 5 atomes de carbone ; une poudre conductrice ; et un solvant aqueux. Cette pâte conductrice est caractérisée en ce que le polymère d'alcool polyvinylique modifié a un degré de polymérisation moyen en viscosité de 200 à 5 000 (inclus), un degré de saponification de 20 % en moles à 99,99 % en moles (inclus) et une teneur de l'unité monomère (A) de 0,05 % en mole à 5 % en moles (inclus).
PCT/JP2012/080994 2011-11-29 2012-11-29 Pâte conductrice et condensateur céramique multicouche Ceased WO2013081077A1 (fr)

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WO2015141623A1 (fr) 2014-03-20 2015-09-24 積水化学工業株式会社 Pâte électroconductrice
WO2017188446A1 (fr) * 2016-04-28 2017-11-02 シャープ株式会社 Pâte conductrice, structure de connexion d'électrode et procédé de fabrication de structure de connexion d'électrode
JP6742877B2 (ja) * 2016-09-28 2020-08-19 株式会社ノリタケカンパニーリミテド 導電性ペースト

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JPS5374588A (en) * 1976-12-14 1978-07-03 Mitsui Petrochem Ind Ltd Copolymer, its production and use
JP2004082526A (ja) * 2002-08-27 2004-03-18 Fuji Photo Film Co Ltd 感熱記録材料
JP2004303748A (ja) * 2003-03-28 2004-10-28 Matsushita Electric Ind Co Ltd グラビア印刷用導電性水性インキ及びそれを用いた積層セラミック電子部品の製造方法
WO2010024245A1 (fr) * 2008-08-27 2010-03-04 株式会社クラレ Polymère de la série alcool vinylique et film le contenant
WO2010113567A1 (fr) * 2009-03-31 2010-10-07 株式会社クラレ Agent d'enrobage contenant un polymère d'alcool vinylique

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JP4968411B2 (ja) * 2009-03-27 2012-07-04 株式会社村田製作所 積層セラミック電子部品の製造方法
KR101141442B1 (ko) * 2009-12-30 2012-05-03 삼성전기주식회사 내부전극용 도전성 페이스트 조성물 및 이를 이용한 적층 세라믹 커패시터의제조방법
CN102169755B (zh) * 2010-02-26 2015-07-15 住友金属矿山株式会社 层叠陶瓷电容器内部电极用导电性糊剂

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JPS5374588A (en) * 1976-12-14 1978-07-03 Mitsui Petrochem Ind Ltd Copolymer, its production and use
JP2004082526A (ja) * 2002-08-27 2004-03-18 Fuji Photo Film Co Ltd 感熱記録材料
JP2004303748A (ja) * 2003-03-28 2004-10-28 Matsushita Electric Ind Co Ltd グラビア印刷用導電性水性インキ及びそれを用いた積層セラミック電子部品の製造方法
WO2010024245A1 (fr) * 2008-08-27 2010-03-04 株式会社クラレ Polymère de la série alcool vinylique et film le contenant
WO2010113567A1 (fr) * 2009-03-31 2010-10-07 株式会社クラレ Agent d'enrobage contenant un polymère d'alcool vinylique

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