Classifications

• • 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
  • C09D11/00—Inks
  • C09D11/52—Electrically conductive inks
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
  • B41M3/006—Patterns of chemical products used for a specific purpose, e.g. pesticides, perfumes, adhesive patterns; use of microencapsulated material; Printing on smoking articles
• • 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
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
• • 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
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • 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
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
• • 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
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks
• • 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
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/36—Inkjet printing inks based on non-aqueous solvents
• • 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
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed

Definitions

• the present invention relates to a method for manufacturing a conductive member.
• Patent Document 1 Japanese Patent Application Laid-Open No. 2004-127851
• the conductive coating is composed of a receiving layer containing at least a porous inorganic filler and a conductive coating formed by applying and drying a metal colloidal solution.
• Patent Document 2 provides a method for expressing conductivity and a conductive member for obtaining conductivity without requiring a firing step which has been conventionally required, and uses water and / or an organic solvent.
• Patent Document 2 provides a method for developing conductivity in which ultrafine metal particles dispersed as a metal colloid and a compound having a halogen in the molecule by ionic bonding are allowed to act to obtain conductivity on a substrate, and the method is used to obtain conductivity.
• the expressed conductive member is described.
• the present invention is a method for producing a conductive member, which comprises applying a conductive ink containing a metal fine particle dispersion onto a substrate and forming a conductive image in a normal temperature environment to obtain a conductive member.
• the metal fine particle dispersion contains the metal fine particle a dispersed in the polymer B,
• the glass transition temperature of the polymer B is equal to or lower than the temperature at which a conductive image is formed.
• the present invention relates to a method for producing a conductive member in which the surface of the base material is porous.
• a conductive image has conventionally been formed by sintering metal fine particles coated on a substrate at a high temperature.
• conductive members it is required to use them for base materials with low heat resistance, flexible base materials, etc., and it is possible to form conductive images with metal fine particles even in a normal temperature environment.
• a method for manufacturing a conductive member having excellent bending resistance In the examples of Patent Document 1, low molecular weight sodium citrate dihydrate is used as a dispersant for the metal colloidal solution, so that the conductivity is not sufficient.
• Patent Document 2 does not have a sintering step at a high temperature, it is necessary to separately use a compound having a halogen in the molecule by ionic bonding to develop conductivity.
• metal thin films generally have low resistance to bending deformation due to external stress. Therefore, in deployment to a flexible base material, bending of the conductive member may cause cracks in the conductive image or peeling of the conductive image from the base material, which may impair conductivity. Therefore, improvement in bending resistance is required.
• the present invention relates to a method for manufacturing a conductive member having a room temperature sintering property and having a conductive image formed with excellent conductivity and bending resistance.
• normal temperature sinterability means that metal fine particles are necked and bonded to each other in a normal temperature environment
• normal temperature environment means “in a temperature environment of 5 ° C. or higher and 45 ° C. or lower”.
• the present inventors use a metal fine particle dispersion containing metal fine particles dispersed in a polymer having a glass transition temperature in a predetermined range, and because the surface of the base material is porous, even in a normal temperature environment. Focusing on the fact that the necking between the metal fine particles progresses and the conductivity is exhibited, and the bending resistance of the obtained conductive member is improved, it was found that the conductive member having excellent conductivity and bending resistance can be obtained. It was. That is, the present invention is a method for manufacturing a conductive member, which comprises applying a conductive ink containing a metal fine particle dispersion onto a substrate and forming a conductive image in a normal temperature environment to obtain a conductive member.
• the metal fine particle dispersion contains the metal fine particle a dispersed in the polymer B,
• the glass transition temperature of the polymer B is equal to or lower than the temperature at which a conductive image is formed.
• the present invention relates to a method for producing a conductive member in which the surface of the base material is porous.
• a method for manufacturing a conductive member having a room temperature sintering property and having a conductive image formed with excellent conductivity and bending resistance it is possible to provide a method for manufacturing a conductive member having a room temperature sintering property and having a conductive image formed with excellent conductivity and bending resistance.
• a conductive ink containing a metal fine particle dispersion is applied onto a base material, and a conductive image is formed in a normal temperature environment to obtain a conductive member.
• the metal fine particle dispersion contains the metal fine particles a dispersed in the polymer B, and the glass transition temperature of the polymer B is equal to or lower than the temperature at which a conductive image is formed, and the surface of the base material. Is porous.
• the metal fine particle dispersion is formed by dispersing the metal fine particles a in the medium with the polymer B.
• the conductive ink used in the present invention contains a metal fine particle dispersion.
• the polymer B in which the metal fine particles are dispersed has a glass transition temperature equal to or lower than the temperature at which a conductive image is formed, and has a flexible structure even in a normal temperature environment. Furthermore, since the surface of the base material used is porous, the polymer B is desorbed from the surface of the metal fine particles by capillary force and migrates to the base material even in a normal temperature environment, and the metal fine particles are necked to each other.
• the metal (metal atom) constituting the metal fine particles a according to the present invention is a Group 4 transition metal such as titanium or zirconium, a Group 5 transition metal such as vanadium or niobium, or a sixth group such as chromium, molybdenum or tungsten.
• Group 10 transition metals such as copper, silver, gold, etc.
• Group 12 transition metals such as zinc, cadmium
• Group 13 metals such as aluminum, gallium, indium, germanium, etc.
• Examples include Group 14 metals such as tin and lead.
• group 4 to group 11 are preferably transition metals of the 4th to 6th periods, more preferably copper, noble metals such as gold, silver, platinum and palladium, and even more preferably copper.
• the type of metal of the conductive member can be confirmed by high frequency inductively coupled plasma emission spectrometry.
• the average particle size of the metal fine particles a in the metal fine particle dispersion is preferably 5 nm or more, more preferably 10 nm or more, further preferably 10 nm or more, from the viewpoint of improving room temperature sinterability and improving conductivity and bending resistance. Is 15 nm or more, and from the viewpoint of forming a conductive image of a fine pattern, it is preferably 100 nm or less, more preferably 80 nm or less, still more preferably 60 nm or less, still more preferably 40 nm or less, still more preferably 35 nm. It is as follows. The average particle size is measured by the method described in Examples.
• the polymer B has a function of dispersing the metal fine particles a.
• the polymer B preferably contains a hydrophilic group from the viewpoint of improving the dispersibility of the metal fine particles, and more preferably has a hydrophilic group in the side chain of the polymer B.
• a hydrophilic group a carboxy group (-COOM), a sulfonic acid group (-SO 3 M), a phosphoric acid group (-OPO 3 M 2 ) and the like are dissociated and hydrogen ions are released to exhibit acidity.
• M represents a hydrogen atom, an alkali metal, ammonium or an organic ammonium.
• the polymer B is preferably a polymer having an anionic group or a polymer having a nonionic group from the viewpoint of improving the room temperature sinterability and the conductivity and bending resistance.
• Examples of the basic structure of the polymer B include vinyl polymers such as acrylic resin, styrene resin, styrene-acrylic resin and acrylic silicone resin; and condensation polymers such as polyester and polyurethane. Of these, vinyl polymers are preferred.
• the polymer B is more preferably a polymer having an anionic group, and further preferably a vinyl polymer having an anionic group.
• Polymer B may be used alone or in combination of two or more. When the polymer B is a copolymer, it may be a block copolymer, a random copolymer, or an alternating copolymer.
• the polymer B may be either water-soluble or water-insoluble, but a water-soluble polymer is preferable from the viewpoint of improving room temperature sinterability, as well as conductivity and bending resistance, and a water-soluble vinyl polymer is preferable. , At least one selected from water-soluble polyester and water-soluble polyurethane is more preferable, and a water-soluble vinyl polymer is further preferable.
• the "water-soluble" of polymer B means that when a polymer that has reached a constant weight after being dried at 105 ° C. for 2 hours is dissolved in 100 g of water at 25 ° C., the dissolved amount is more than 10 g. means.
• the "water-insoluble" of the polymer B means that when the polymer which has reached a constant weight after being dried at 105 ° C. for 2 hours is dissolved in 100 g of water at 25 ° C., the dissolved amount is 10 g or less.
• the polymer B is a polymer having an anionic group
• the dissolved amount thereof is the dissolved amount when the anionic group of the polymer B is 100% neutralized with sodium hydroxide.
• the polymer B is a polymer having a cationic group
• the dissolved amount is the dissolved amount when the cationic group of the polymer B is 100% neutralized with hydrochloric acid.
• the polymer B preferably has a carboxy group in the side chain of the polymer B from the viewpoint of improving the dispersibility of the metal fine particles and improving the conductivity and bending resistance, and more preferably the carboxy. It is a water-soluble vinyl polymer containing a structural unit derived from a monomer (b-1) having a group and a structural unit derived from a monomer (b-2) having a polyalkylene glycol segment.
• the carboxy group contained in the monomer (b-1) is as described above.
• Specific examples of the monomer (b-1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and 2-methacryloyloxymethylsuccinic acid; maleic acid, itaconic acid, fumaric acid, citraconic acid, and the like. Examples thereof include unsaturated dicarboxylic acids.
• the unsaturated dicarboxylic acid may be anhydrous.
• the monomer (b-1) may be used alone or in combination of two or more.
• the monomer (b-1) is preferably at least one selected from (meth) acrylic acid and maleic acid from the viewpoint of improving the dispersibility of the metal fine particles and improving the conductivity and bending resistance. More preferably, it is (meth) acrylic acid.
• (meth) acrylic acid means at least one selected from acrylic acid and methacrylic acid.
• (Meta) acrylic acid” in the following is also synonymous.
• the monomer (b-2) is preferably a monomer into which a polyalkylene glycol segment can be introduced as a side chain of the polymer B from the viewpoint of improving the dispersibility of the metal fine particles and improving the conductivity and bending resistance.
• Examples of the monomer include polyalkylene glycol monoesters of (meth) acrylic acid.
• the monomer (b-2) may be used alone or in combination of two or more.
• the polyalkylene glycol segment of the monomer (b-2) preferably contains a unit derived from an alkylene oxide having 2 to 4 carbon atoms.
• the alkylene oxide include ethylene oxide, propylene oxide and butylene oxide.
• the number of units derived from the alkylene oxide in the polyalkylene glycol segment is preferably 2 or more, more preferably 5 or more, still more preferably 10 or more, and preferably 100 or less, more preferably 70 or less, still more preferably. It is 50 or less.
• the polyalkylene glycol segment is preferably a copolymer containing a unit derived from ethylene oxide and a unit derived from propylene oxide from the viewpoint of improving the dispersibility of the metal fine particles and improving the conductivity and bending resistance.
• the molar ratio [EO / PO] of ethylene oxide units (EO) to propylene oxide units (PO) is preferably 60/40 or more, more preferably 65/35 or more, still more preferably 70/30 or more, and It is preferably 90/10 or less, more preferably 85/15 or less, and even more preferably 80/20 or less.
• the copolymer containing the unit derived from ethylene oxide and the unit derived from propylene oxide may be any of a block copolymer, a random copolymer, and an alternating copolymer.
• b-2 Specific examples of commercially available monomer (b-2) include NK ester AM-90G, AM-130G, AMP-20GY, 230G, M-20G, and 40G of Shin Nakamura Chemical Industry Co., Ltd. , 90G, 230G, etc., NOF Corporation's Blemmer PE-90, 200, 350, etc., PME-100, 200, 400, 1000, 4000, etc., PP-500, 800, 800, etc. Examples thereof include 1000 and the like, AP-150, 400, 550 and the like, 50PEP-300, 50PEEP-800B, 43PAPE-600B and the like.
• the polymer B is added to the structural unit derived from the monomer (b-1) and the structural unit derived from the monomer (b-2) from the viewpoint of improving the dispersibility of the metal fine particles and improving the conductivity and bending resistance. Further, it is preferably a water-soluble vinyl polymer containing a structural unit derived from the hydrophobic monomer (b-3).
• the "hydrophobicity" of the monomer (b-3) means that when the monomer is dissolved in 100 g of ion-exchanged water at 25 ° C., the amount of the monomer dissolved is less than 10 g.
• the amount of the monomer (b-3) dissolved is preferably 5 g or less, more preferably 1 g or less, from the viewpoint of improving the dispersibility of the metal fine particles and improving the conductivity and bending resistance.
• the monomer (b-3) is preferably at least one selected from an aromatic group-containing monomer and a (meth) acrylate having a hydrocarbon group derived from an aliphatic alcohol having 1 to 22 carbon atoms, and more preferably. It is an aromatic group-containing monomer.
• the term "(meth) acrylate” is at least one selected from acrylates and methacrylates. "(Meta) acrylate” in the following is also synonymous.
• the monomer (b-3) may be used alone or in combination of two or more.
• the aromatic group-containing monomer is preferably a vinyl monomer having an aromatic group having 6 or more and 22 or less carbon atoms, which may have a substituent containing a heteroatom, and more preferably a styrene-based monomer and an aromatic group. It is at least one selected from group-containing (meth) acrylates.
• the molecular weight of the aromatic group-containing monomer is preferably less than 500. Examples of the styrene-based monomer include styrene, ⁇ -methylstyrene, 2-methylstyrene, 4-methylstyrene, divinylbenzene and the like, but styrene and ⁇ -methylstyrene are preferable.
• the aromatic group-containing (meth) acrylate phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like are preferable, and benzyl (meth) acrylate is more preferable.
• the monomer (b-3) is more preferably a styrene-based monomer, and even more preferably styrene or ⁇ -methylstyrene, from the viewpoint of improving the dispersibility of the metal fine particles and improving the conductivity and bending resistance. , 2-Methylstyrene and 4-methylstyrene, and even more preferably at least one selected from styrene and ⁇ -methylstyrene.
• the content of the structural unit derived from (b-3) is as follows from the viewpoint of improving the dispersibility of the metal fine particles and improving the conductivity and bending resistance.
• the content of the monomer (b-1) is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more, and preferably 40 mol% or less, more preferably 35 mol.
• the content of the monomer (b-2) is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 7 mol% or more, and preferably 30 mol% or less, more preferably 20 mol. % Or less, more preferably 15 mol% or less.
• the content of the monomer (b-3) is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 65 mol% or more, and preferably 90 mol% or less, more preferably 85 mol. % Or less, more preferably 80 mol% or less.
• the polymer B is preferably water-soluble and contains a structural unit derived from (meth) acrylic acid as the monomer (b-1) and a structural unit derived from the polyalkylene glycol monoester of (meth) acrylic acid as the monomer (b-2).
• a vinyl polymer more preferably a structural unit derived from (meth) acrylic acid as the monomer (b-1), and a structural unit derived from the polyalkylene glycol monoester of (meth) acrylic acid as the monomer (b-2).
• a water-soluble vinyl polymer containing a structural unit derived from a styrene-based monomer as the monomer (b-3).
• the polymer B a polymer obtained by copolymerizing a raw material monomer containing a monomer (b-1), a monomer (b-2) and a monomer (b-3) by a known method may be used, and a commercially available product may be used. May be good.
• Examples of commercially available products of the polymer B include DISPERBYK-190 and 2015 manufactured by BYK.
• the content of the water-soluble vinyl polymer in the polymer B improves the dispersibility of the metal fine particles and the room temperature sintering property, as well as the conductivity and the bending resistance. From the viewpoint of allowing the particles to grow, it is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass or less, still more preferably. Is 100% by mass.
• the number average molecular weight of the polymer B is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more, and preferably 100,000 or less, more preferably 50,000 or less. It is even more preferably 30,000 or less, even more preferably 10,000 or less, and even more preferably 7,000 or less.
• the number average molecular weight of polymer B can be measured by gel permeation chromatography using monodisperse polystyrene having a known molecular weight as a standard substance.
• the acid value of the polymer B is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and preferably 200 mgKOH / g or less, more preferably 100 mgKOH / g or less, further. It is preferably 50 mgKOH / g or less, and even more preferably 30 mgKOH / g or less.
• the glass transition temperature of the polymer B is not more than the temperature at which a conductive image is formed, preferably 10 ° C. or less, more preferably 10 ° C. or less, from the viewpoint of improving room temperature sinterability and improving conductivity and bending resistance. 0 ° C or lower, more preferably -10 ° C or lower, even more preferably -30 ° C or lower, even more preferably -50 ° C or lower, and preferably -100 ° C or higher, more preferably -90 ° C or higher, further. It is preferably ⁇ 80 ° C. or higher.
• the glass transition temperature of Polymer B is measured by the method described in Examples.
• the glass temperature is measured based on the peak. To do. Further, when two or more kinds of polymers are used as the polymer B, if the polymers are not compatible with each other and two or more peaks are observed by the method described in Examples, the glass transition of each polymer constituting the polymer B is observed. The temperature is measured and calculated by a weighted average.
• the present form of the polymer B in the metal fine particle dispersion and the conductive ink is a form in which the polymer B is adsorbed on the metal fine particle a, a form in which the metal fine particle a is contained in the polymer B, and a metal fine particle inclusion (capsule) form.
• the polymer B is not adsorbed on the metal fine particles a. From the viewpoint of improving the conductivity and bending resistance, the form in which the metal fine particles a are contained in the polymer B is preferable, and the state in which the metal fine particles a are contained in the polymer B is more preferable.
• the mass ratio of polymer B to the total amount of polymer B and metal in the metal fine particle dispersion [polymer B / (polymer B + metal)] is from the viewpoint of improving room temperature sinterability and from the viewpoint of improving conductivity and bending resistance. Therefore, it is preferably 0.01 or more, more preferably 0.03 or more, further preferably 0.05 or more, and preferably 0.3 or less, more preferably 0.2 or less, still more preferably 0.15. It is as follows.
• the mass ratio [polymer B / (polymer B + metal)] is calculated from the mass of polymer B and metal measured by the method described in Examples using a differential thermogravimetric simultaneous measuring device (TG / DTA). ..
• the content of the metal in the conductive ink is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, still more preferably 7% by mass or more. From the viewpoint of improving the bending resistance, the content is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, still more preferably 15% by mass or less.
• the metal content in the conductive ink is measured and calculated by the method described in the examples.
• the preferred numerical range of the mass ratio of polymer B to the total amount of polymer B and metal in the conductive ink is the mass ratio [polymer B / (polymer B + metal)] in the above-mentioned metal fine particle dispersion. )] Is the same range as the preferable numerical range.
• the mass ratio [polymer B / (polymer B + metal)] in the conductive ink is the same as the mass ratio [polymer B / (polymer B + metal)] in the metal fine particle dispersion described above, and the differential thermogravimetric simultaneous measurement device (TG /). Calculated from the mass of polymer B and metal measured using DTA).
• the conductive ink preferably contains hydroxyketone from the viewpoint of improving conductivity and bending resistance.
• the hydroxyketone has a carbonyl group and a hydroxy group in the molecule, and since the hydroxyketone is coordinated and adsorbed on the metal fine particles by these functional groups, the dispersion stability of the metal fine particles is improved by the chelating effect.
• Examples of the hydroxyketone include ⁇ -hydroxyketone and ⁇ -hydroxyketone.
• monohydroxyacetone (1-hydroxy-2-propanone), 1-hydroxy-2-butanone, and 3-hydroxy-2- Butanone, 3-hydroxy-3-methyl-2-butanone, 1-hydroxy-2-pentanone, 3-hydroxy-2-pentanone, 2-hydroxy-3-pentanone, 4-hydroxy-4-methyl-2-pentanone, Examples include 3-hydroxy-2-hexanone, 2-hydroxy-3-hexanone, 4-hydroxy-3-hexanone, 4-hydroxy-3-heptanone, 3-hydroxy-4-heptanone, 5-hydroxy-4-octanone and the like. Be done.
• One type of hydroxyketone may be used alone, or two or more types may be used in combination.
• ⁇ -hydroxyketone is preferable, and monohydroxyacetone is more preferable, from the viewpoint of improving the dispersion stability of the metal fine particles and improving the conductivity and bending resistance.
• monohydroxyacetone is a small molecule, it is considered that steric hindrance is small and it can be closely coordinated and adsorbed on the surface of metal fine particles.
• monohydroxyacetone has hydrophobic methyl groups and hydrophilic hydroxymethyl groups on both sides of the carbonyl group, it has an excellent balance of hydrophobicity and can be adsorbed on the surface of metal fine particles to improve dispersion stability. it can.
• the content of hydroxyketone in the conductive ink is preferably 0.05% by mass or more, more preferably 0. From the viewpoint of improving the dispersion stability of the metal fine particles and improving the conductivity and bending resistance. 1% by mass or more, more preferably 0.3% by mass or more, and preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less. , More preferably 1% by mass or less.
• the mass ratio of hydroxyketone to metal [hydroxyketone / metal] in the conductive ink is preferably 0.005 or more, more preferably 0.01 or more, still more preferably 0.01 or more, from the viewpoint of improving the dispersion stability of the metal fine particles.
• the conductive ink preferably contains a monocarboxylic acid having 1 to 24 carbon atoms or a polycarboxylic acid, and more preferably a monocarboxylic acid having 1 to 24 carbon atoms (hereinafter,). , Simply referred to as "monocarboxylic acid").
• the carboxylic acid may have a functional group other than the carboxy group. Examples of the functional group include a functional group having a coordination property with respect to metal fine particles such as a functional group containing a halogen atom, a functional group containing at least one hetero atom such as a hydroxy group and a thiol group.
• the carbon number of the monocarboxylic acid is preferably 1 or more, and preferably 20 or less, more preferably 16 or less, still more preferably 10 or less, still more preferably 8 or less, still more preferably 6 or less.
• the monocarboxylic acid is preferably a saturated aliphatic monocarboxylic acid from the viewpoint of improving the dispersion stability of the metal fine particles and improving the conductivity and bending resistance.
• Examples of the saturated aliphatic monocarboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, capric acid, capric acid, lauric acid, palmitic acid and other linear aliphatic carboxylic acids. From the same viewpoint as described above, it is preferably at least one selected from formic acid, acetic acid and propionic acid, more preferably at least one selected from formic acid and formic acid, and even more preferably acetic acid.
• the content of the monocarboxylic acid in the conductive ink is preferably 0.05% by mass or more, more preferably 0, from the viewpoint of improving the dispersion stability of the metal fine particles and improving the conductivity and bending resistance. .1% by mass or more, more preferably 0.3% by mass or more, and preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass. Hereinafter, it is even more preferably 1% by mass or less.
• the mass ratio of monocarboxylic acid to metal in the conductive ink [monocarboxylic acid / metal] is preferably 0.005 or more, more preferably 0.01 or more, and further, from the viewpoint of improving the dispersion stability of the metal fine particles. It is preferably 0.02 or more, more preferably 0.03 or more, and preferably 1.5 or less, more preferably 1 or less, still more preferably 0.5 or less, still more preferably 0.1 or less. is there.
• the content of the monocarboxylic acid in the conductive ink and the mass ratio [monocarboxylic acid / metal] are measured and calculated by the method described in Examples.
• the conductive ink preferably contains an aqueous solvent from the viewpoint of improving conductivity and bending resistance.
• the aqueous solvent preferably contains water as a main component, and may further contain an organic solvent C.
• the organic solvent C include aliphatic alcohols having 1 to 4 carbon atoms such as ethanol, 1-propanol, 2-propanol and propylene glycol; and ketones having 3 to 8 carbon atoms other than hydroxy ketones such as acetone and methyl ethyl ketone.
• Ethers such as tetrahydrofuran: Alkyl acetate (C1 to C3) esters such as ethyl acetate and propyl acetate can be mentioned.
• the boiling point of the organic solvent C is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, further preferably 60 ° C. or higher, and preferably 230 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 150 ° C. or lower. , More preferably 100 ° C. or lower, even more preferably 90 ° C. or lower, and even more preferably 80 ° C. or lower.
• the boiling point of the organic solvent C is a weighted average value weighted by the content (mass%) of each organic solvent.
• the organic solvent C is preferably at least one selected from acetone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate, 1-propanol and propylene glycol from the viewpoint of improving conductivity and bending resistance, and more preferably propylene glycol.
• the content of water in the aqueous solvent is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and preferably 95% by mass or less. It is more preferably 90% by mass or less, still more preferably 85% by mass or less.
• the content of the organic solvent C in the conductive ink is preferably 3% by mass or more, more preferably 7% by mass or more, still more preferably 10% by mass or more, from the viewpoint of improving the conductivity and bending resistance. Then, it is preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less.
• the mass ratio of the organic solvent C to the metal in the conductive ink [organic solvent C / metal] is preferably 0.1 or more, more preferably 0.5 or more, and further, from the viewpoint of improving conductivity and bending resistance. It is preferably 1 or more, and preferably 5 or less, more preferably 3 or less, still more preferably 2 or less.
• the conductive ink preferably contains substantially no counterion of metal ions.
• substantially free means that the content of counterions in the conductive ink is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 3 ppm or less, still more preferably 1 ppm or less, and more. More preferably, it means that it is 0 ppm.
• the conductive ink when there is a possibility that nitrate ions derived from the metal raw material compound used in the production of the metal fine particle dispersion may be mixed as counter ions of the metal ions, the conductive ink should be substantially free of nitrate ions. Is preferable.
• the conductive ink is a polymer dispersant other than polymer B, a surfactant, a moisturizer, a wetting agent, a penetrant, and a viscosity, which are usually used for the conductive ink, if necessary, as long as the effect of the present invention is not impaired.
• Various additives such as a modifier, an antifoaming agent, a preservative, a fungicide, and a rust preventive may be contained.
• the average particle size of the metal fine particles a in the conductive ink is preferably the same as the average particle size of the metal fine particle dispersion described above, and a preferred embodiment of the average particle size is also the average particle size of the metal fine particle dispersion. It is the same as the preferred embodiment.
• the viscosity of the conductive ink at 32 ° C. is preferably 2 mPa ⁇ s or more, more preferably 3 mPa ⁇ s or more, still more preferably 4 mPa ⁇ s or more, and preferably 30 mPa ⁇ s or more from the viewpoint of conductivity and bending resistance.
• the viscosity of the ink can be measured using an E-type viscometer.
• the pH of the conductive ink at 20 ° C. is preferably 4.0 or more, more preferably 4.5 or more, still more preferably 5.0 or more, from the viewpoint of conductivity and bending resistance. Further, from the viewpoint of member resistance and skin irritation, the pH is preferably 11 or less, more preferably 10 or less, still more preferably 9.5 or less.
• the pH of the ink can be measured by a conventional method.
• the conductive ink according to the present invention can be obtained by preparing a metal fine particle dispersion in advance, and then mixing, if necessary, a hydroxy ketone, a carboxylic acid, an aqueous solvent, or the like and stirring the mixture.
• the metal fine particle dispersion is prepared by mixing a metal raw material compound A, a polymer B and a reducing agent to reduce the metal raw material compound A (i), adding a dispersion medium to the metal fine particles prepared in advance by a known method, and adding a dispersion medium. It can be obtained by the mixing method (ii) or the like. Above all, the method (i) is preferable from the viewpoint of improving the dispersion stability of the metal fine particles.
• the metal raw material compound A is reduced by a reducing agent to form metal fine particles a dispersed in the polymer B.
• the metal raw material compound A, the polymer B, and the reducing agent can be mixed by a known method, and the mixing order is not particularly limited.
• the above-mentioned aqueous solvent may be further used, and when an aqueous solvent is used, the aqueous solvent may be used as a dispersion medium for the obtained metal fine particle dispersion.
• the reduction reaction is preferably in a temperature range of 10 ° C. or higher, more preferably 20 ° C. or higher, still more preferably 30 ° C. or higher, and preferably 70 ° C. or lower, more preferably 60 ° C. or lower, still more preferably 50 ° C. or lower. It is preferable to carry out with.
• the reduction reaction may be carried out in an air atmosphere or in an inert gas atmosphere such as nitrogen gas.
• the metal raw material compound A is not particularly limited as long as it is a compound containing the above-mentioned metal, and examples thereof include metal salts of inorganic or organic acids, metal oxides, metal hydroxides, metal sulfides, and metal halides. ..
• the metal salt include metal salts of inorganic acids such as nitrates, nitrites, sulfates, carbonates, ammonium salts and perchlorates; and metal salts of organic acids such as acetates.
• the metal raw material compound A one type can be used alone or two or more types can be mixed and used.
• At least one selected from metal salts and metal oxides of inorganic or organic acids is preferable, and at least one selected from metal salts and metal oxides of nitric acid is more preferable, and more preferably.
• It is a metal oxide.
• the metal raw material compound A is a metal oxide
• the obtained dispersion does not contain counterions of metal ions as impurities, and a metal fine particle dispersion can be obtained without requiring purification such as dialysis.
• the metal oxide is preferably an oxide of a transition metal of Group 4 to Group 11 and period 4 to 6, and more preferably oxidation of a noble metal such as copper, gold, silver, platinum, or palladium. It is a product, more preferably at least one oxide selected from gold, silver, copper and palladium, still more preferably at least one selected from gold oxide, silver oxide and copper oxide, and even more preferably. Is at least one selected from silver oxide.
• the reducing agent is not particularly limited, and either an inorganic reducing agent or an organic reducing agent can be used.
• organic reducing agents alcohols such as ethylene glycol and propylene glycol; aldehydes such as formaldehyde, acetaldehyde and propionaldehyde; acids such as ascorbic acid and citric acid and salts thereof; ethanolamine, N-methylethanolamine, N, N-Dimethylethanolamine (2- (dimethylamino) ethanol), N, N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, propanolamine, N, N-dimethylpropanolamine, butanolamine, hexanolamine Alkanolamine, propylamine, butylamine, hexylamine, diethylamine, dipropylamine, dimethylethylamine, diethylmethylamine, alkylamine such as triethylamine, ethylene
• the inorganic reducing agent examples include borohydride salts such as sodium borohydride and ammonium borohydride; aluminum hydride salts such as lithium aluminum hydride and potassium aluminum hydride; hydrazines such as hydrazine and hydrazine carbonate; hydrogen gas and the like. Can be mentioned.
• the reducing agent may be used alone or in combination of two or more.
• the reducing agent is preferably an organic reducing agent, more preferably at least one selected from alcohols and amines, and even more preferably from ethylene glycol, propylene glycol, and alkanolamine having 2 or more and 6 or less carbon atoms. At least one selected, and even more preferably at least one selected from propylene glycol and N, N-dimethylethanolamine.
• propylene glycol is used as the reducing agent, propylene glycol is oxidized during the reduction reaction to produce monohydroxyacetone. Therefore, by adjusting the conditions of the reduction reaction, monohydroxyacetone and propylene glycol in the metal fine particle dispersion can be used. The content can be adjusted.
• propylene glycol also has a function as a dispersion medium for the metal fine particle dispersion, it does not require a separate step of adding a dispersion medium, which is preferable from the viewpoint of ease of production.
• the metal fine particle dispersion further contains a monocarboxylic acid
• the above-mentioned monohydroxyacetone is further oxidized during the reduction reaction by adjusting the conditions of the reduction reaction using propylene glycol as a reducing agent. Since acetic acid is produced, a separate step of adding a monocarboxylic acid is not required, which is preferable from the viewpoint of ease of production.
• the metal fine particle dispersion obtained in the method (i) may be further purified from the viewpoint of removing impurities such as an unreacted reducing agent and excess polymer B that does not contribute to the dispersion of the metal fine particles.
• the method for purifying the metal fine particle dispersion is not particularly limited, and examples thereof include membrane treatment such as dialysis and ultrafiltration; and centrifugation treatment. Above all, membrane treatment is preferable, and dialysis is more preferable, from the viewpoint of efficiently removing impurities. Regenerated cellulose is preferable as the material of the dialysis membrane used for dialysis.
• the fractional molecular weight of the dialysis membrane is preferably 1,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, and preferably 100,000 or less, from the viewpoint of efficiently removing impurities. , More preferably 70,000 or less.
• a conductive ink is applied onto a base material from the viewpoint of improving the room temperature sinterability and the conductivity and bending resistance, and the conductive member is conductive in a room temperature environment.
• An image is formed to obtain a conductive member.
• the metal fine particle dispersion can be directly applied as a conductive ink on the substrate.
• the temperature at which the conductive image is formed is in the above-mentioned normal temperature range (5 ° C. or higher and 45 ° C. or lower) from the viewpoint of improving conductivity and bending resistance, preferably 10 ° C. or higher, and more preferably 15 ° C. or higher. It is more preferably 20 ° C. or higher, and preferably 40 ° C. or lower, more preferably 35 ° C. or lower, still more preferably 30 ° C. or lower.
• the base material used in the present invention has a porous surface.
• the average pore size of the porous surface of the base material is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 20 nm or more, from the viewpoint of improving the room temperature sinterability of the metal fine particles and improving the conductivity and bending resistance. It is 30 nm or more, and preferably 200 nm or less, more preferably 150 nm or less, still more preferably 100 nm or less.
• the average pore size of the porous surface of the base material is measured by the method described in Examples.
• the base material is cellulose, polytetrafluoroethylene, stretched polytetrafluoroethylene, polyolefin, polyester, polyamide, polyether, polysulfone, polyethersulfone, polyvinylidene fluoride, polyvinyl chloride, polystyrene, polyethylene, polypropylene, polyacrylonitrile, Examples thereof include (meth) acrylic polymers, various polymers such as polyurethane; various glasses; various ceramics, or a porous substrate composed of a combination thereof. Examples of the form of the base material include coated paper, glossy paper, plain paper, glossy film and the like.
• the base material may be at least porous on the surface of the base material, but is void-type porous from the viewpoint of improving the room temperature sintering property of the metal fine particles and improving the conductivity and bending resistance.
• a base material having a fine particle-containing layer as a layer on the surface of the base material (hereinafter, also referred to as “void-type base material”) is preferable.
• the void type substrate is preferably obtained by forming a fine particle-containing layer composed of fine particles and a water-soluble polymer (binder) on the surface of the support.
• the polymer B and the medium are absorbed by the capillary force due to the voids between the fine particles, and normal temperature sintering property, high conductivity and bending resistance can be exhibited.
• the fine particles include inorganic fine particles and organic fine particles, preferably one or more inorganic fine particles selected from silica and alumina, and more preferably one or more porous inorganic fine particles selected from silica and alumina. is there.
• the water-soluble polymer (binder) include polyvinyl alcohol and the like.
• the support of the void type base material one containing paper, a resin film, a composite thereof and the like is preferable, and paper is more preferable from the viewpoint of versatility.
• the base material used in the present invention is a base material in which an inorganic fine particle-containing layer is formed on the surface of the support from the viewpoint of improving the room temperature sintering property of the metal fine particles and improving the conductivity and bending resistance. It is more preferable that the base material has an inorganic fine particle-containing layer formed on the surface of the paper support.
• the substrate used in the present invention preferably has a high surface smoothness from the viewpoint of improving conductivity.
• the smoothness of the surface of the base material can be indexed by an 8 ° gloss value, and from the same viewpoint as described above, the 8 ° gloss value is preferably 20 or more, and preferably 50 or less, more preferably 50 or less. It is 40 or less, more preferably 30 or less.
• the 8 ° gloss value on the surface of the substrate is measured by the method described in Examples.
• a commercially available paper for exclusive use of an inkjet can be used as the base material according to the present invention. Examples of such a base material include, for example, Seiko Epson Corporation, trade name: photo paper ⁇ gloss>, model number: KA4100PSKR.
• the method of applying conductive ink including inkjet printing, screen printing, flexo printing, gravure printing, offset printing, dispenser printing, slot die coating, dip coating, spray coating, spin coating, doctor braiding, and knife edge coating. , Bar coating and the like.
• the inkjet printing method is preferable from the viewpoint of improving conductivity and bending resistance.
• the conductive ink can be loaded into the inkjet printing apparatus and ejected as ink droplets onto the substrate to form a conductive image.
• the inkjet printing apparatus includes a thermal type and a piezo type, but the piezo type is preferable.
• the head temperature of the inkjet head is not particularly limited as long as it is within the temperature range for forming the above-mentioned conductive image, but is preferably 15 ° C. or higher, more preferably 20 ° C. from the viewpoint of improving conductivity and bending resistance. Above, it is more preferably 25 ° C. or higher, and preferably 45 ° C. or lower, more preferably 40 ° C. or lower, still more preferably 35 ° C.
• the head voltage of the inkjet head is preferably 5 V or more, more preferably 10 V or more, further preferably 15 V or more, and preferably 40 V or less, more preferably 35 V or less, still more preferable. Is 30 V or less.
• the drive frequency of the head is preferably 1 kHz or more, more preferably 5 kHz or more, still more preferably 10 kHz or more, and preferably 50 kHz or less, more preferably 40 kHz or less, still more preferably, from the viewpoint of printing efficiency or the like. It is 35 kHz or less.
• the amount of ejected droplets of the conductive ink is preferably 5 pL or more, more preferably 10 pL or more per drop from the viewpoint of maintaining the accuracy of the landing position of the ink droplets and improving the conductivity and bending resistance. Yes, and preferably 30 pL or less, more preferably 20 pL or less.
• Application amount of conductive ink to the substrate, as a solid content is preferably 0.5 g / m 2 or more, more preferably 1 g / m 2 or more, more preferably 2 g / m 2 or more, and, preferably It is 20 g / m 2 or less, more preferably 15 g / m 2 or less, still more preferably 10 g / m 2 or less.
• the resolution is preferably 200 dpi or more, more preferably 300 dpi or more, and preferably 1,000 dpi or less, more preferably 800 dpi or less, still more preferably 600 dpi or less.
• the “resolution” in the present specification means the number of dots per inch (2.54 cm) formed on the base material.
• “resolution is 600 dpi” corresponds to the case where ink droplets are ejected onto a substrate using a line head in which the number of nozzle holes per length of a nozzle row is 600 dpi (dots / inch).
• a row of 600 dpi dots per inch is formed in a direction perpendicular to the transport direction of the base material, and when ink droplets are ejected while moving the base material in the transport direction, the ink droplets are also ejected on the base material in the transport direction. It means that a row of dots of 600 dpi per inch is formed.
• the resolution in the direction perpendicular to the transport direction of the base material and the resolution in the transport direction are expressed as the same value.
• the coating temperature is the same as the coating temperature or in the range of the normal temperature.
• it may have a drying step of drying the ink coating film on the substrate at a higher temperature, it is preferable not to have the drying step from the viewpoint of productivity of the conductive member.
• the contact angle of water in the conductive image formed on the conductive member is preferably 70 ° or more, more preferably 80 ° or more, still more preferably 80 ° or more, from the viewpoint of adhesion between the conductive member and other constituent members. It is 90 ° or more, more preferably 95 ° or more, and even more preferably 100 ° or more.
• the water contact angle of the conductive image is measured by the method described in the examples.
• the film thickness of the conductive image is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, still more preferably 0.5 ⁇ m or more, and preferably 5 ⁇ m or less, more preferably 4 ⁇ m or less, still more preferably 3 ⁇ m. It is as follows.
• the volume resistivity ⁇ v of the conductive image is preferably 5 ⁇ 10 -5 ⁇ ⁇ cm or less, more preferably 4.5 ⁇ 10 -5 ⁇ ⁇ cm or less, and further preferably 4.0 ⁇ 10 -5 ⁇ ⁇ cm. Below, it is even more preferably 3.5 ⁇ 10 -5 ⁇ ⁇ cm or less, and even more preferably 3.0 ⁇ 10 -5 ⁇ ⁇ cm or less.
• the volume resistivity ⁇ v of the conductive image is measured by the method described in the examples.
• the method of the present invention has room temperature sintering properties and is excellent in conductivity and bending resistance, and is therefore useful for forming wirings, electrodes, etc. in various fields.
• RFID radio frequency identifier
• capacitor such as MLCC (multilayer ceramic capacitor)
• electronic paper image display device such as liquid crystal display and organic EL display; organic EL element; organic transistor; printed wiring board, flexible wiring board Wiring boards such as; organic solar cells; sensors such as flexible sensors; bonding agents such as solders and the like.
• Tg glass transition temperature
• Polymer B was dried under reduced pressure at 100 ° C. and 8 KPa for 24 hours using a vacuum dryer (manufactured by Yamato Scientific Co., Ltd., model: DP-33). .. Weigh 0.01 to 0.02 g of this polymer B into an aluminum pan using a differential scanning calorimeter (manufactured by TA Instruments Japan Co., Ltd., model: Q-200) and measure it at 200 ° C. The temperature was raised to -80 ° C at a temperature lowering rate of 10 ° C./min. Then, the measurement was carried out while raising the temperature to 150 ° C. at a heating rate of 10 ° C./min. The temperature at the intersection of the extension of the baseline below the maximum peak temperature of heat absorption and the tangent line indicating the maximum inclination from the rising portion of the peak to the peak of the peak was defined as the glass transition temperature of the polymer B.
• a differential thermogravimetric simultaneous measurement device (TG / DTA) (Co., Ltd.) measures the metal fine particle dispersion or conductive ink. Using Hitachi High-Tech Science Co., Ltd., trade name: STA7200RV), weigh 10 mg of a sample into an aluminum pan cell, raise the temperature from 35 ° C to 550 ° C at a heating rate of 10 ° C / min, and air flow of 50 mL / min. The mass loss was measured below. The mass reduction from 35 ° C. to 230 ° C. is the mass of the medium, the mass reduction from 230 ° C. to 550 ° C. is the mass of polymer B, and the residual mass at 550 ° C. is the mass of metal. The metal content (%) and the polymer B content (%) in the ink were calculated.
• the photographed STEM image was processed by image analysis software (Asahi Kasei Engineering Co., Ltd., A image-kun), and the "circle equivalent diameter" of each of 200 particles was calculated and used as the particle size of each particle.
• image analysis software Alignment software (Asahi Kasei Engineering Co., Ltd., A image-kun)
• the average value of the remaining 90% was obtained, and the value was used as the average particle size of the metal fine particles a.
• the surface of the base material is subject to the conditions of a field emission scanning electron microscope (FE-SEM) (Hitachi Co., Ltd., S-4800), SEM mode, and an accelerating voltage of 10 KV.
• FE-SEM field emission scanning electron microscope
• the surface SEM image was taken.
• the obtained SEM image was processed in a range of 1 ⁇ m 2 by image analysis software (ImageJ, manufactured by National Institutes of Health, USA), and the equivalent circle diameter of each hole was calculated and used as the hole diameter of each hole.
• the values of the upper 5% and the lower 5% were removed, and the average value of the remaining 90% was obtained, and the value was used as the average pore size of the porous surface of the base material.
• the flask was placed in a water bath at 40 ° C., and after the internal temperature of the flask reached 40 ° C., stirring was performed for 2 hours, and then air cooling was performed to obtain a dark brown liquid.
• the obtained dark brown liquid is put into a 100 mL angle rotor and centrifuged at 3,000 rpm for 20 minutes using a high-speed cooling centrifuge (manufactured by Koki Holdings Co., Ltd., trade name: himaCR22G, set temperature 20 ° C.).
• the liquid layer portion was filtered with a needleless syringe (manufactured by Terumo Co., Ltd.) having a capacity of 25 mL to which a 5 ⁇ m membrane filter (manufactured by Sartorius, trade name: minisalt) was attached to obtain a silver fine particle dispersion 1.
• a needleless syringe manufactured by Terumo Co., Ltd.
• a 5 ⁇ m membrane filter manufactured by Sartorius, trade name: minisalt
• Preparation Example 2 Silver fine particle dispersion 2 was obtained in the same manner except that BYK-2015 was changed to 16 g of dextrin hydrate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., special grade reagent) in Preparation Example 1.
• Preparation Example 3 In a 1 L glass spinner flask (manufactured by PYREX), 144 g of silver nitrate as the metal raw material compound A, 20 g of BYK-2015 (40 mass% solid content aqueous solution) as the polymer B, and 130 g of ion-exchanged water were put into the 1 L glass spinner flask, and a magnetic stirrer was added. The mixture was stirred at room temperature until it became visually transparent to obtain a mixed solution.
• DMAE N, N-dimethylethanolamine
• This tube was immersed in 40 L of ion-exchanged water in a 50 L stainless steel beaker, and the water temperature was maintained at 20 to 25 ° C. and stirred for 1 hour. Then, the operation of exchanging the entire amount of the ion-exchanged water every hour was repeated three times, and then the dialysis was completed with stirring for 24 hours to obtain a purified silver fine particle dispersion.
• the silver fine particle dispersion obtained above was concentrated under reduced pressure at 60 ° C. so that the silver concentration became 35% to obtain a silver fine particle dispersion 3.
• Preparation Example 4 Silver fine particle dispersion 4 was obtained in the same manner except that BYK-2015 was changed to 16 g of succinic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) in Preparation Example 1.
• the yield of the metal fine particle a was measured by the method shown below, and the content of each component in the metal fine particle dispersion and the average particle size of the metal fine particle a were determined. It was measured by the method described above. The results are shown in Table 1.
• yield of the metal fine particles a 100 ⁇ [1- (mass (g) of dried precipitate component / mass (g) of metal contained in 10 g of obtained metal fine particle dispersion)]
• Example 1 (Ink 1) 20 g of silver fine particle dispersion 1 (silver content 37.4%) was put into a 100 mL polyethylene screw tube. Next, 54.8 g of ion-exchanged water was added, and the mixture was stirred at room temperature for 0.5 hours using a magnetic stirrer to obtain ink 1 having the composition shown in Table 2.
• Production Examples 2 to 7 (inks 2 to 7)
• the silver fine particle dispersion shown in Table 2 was used instead of the silver fine particle dispersion 1, and the amount of monohydroxyacetone, acetic acid, or ion-exchanged water was changed as shown in Table 2 to change the composition of the ink.
• Each ink was obtained in the same manner except for the adjustment.
• Example 1 Ink printing equipped with an inkjet head (manufactured by Kyocera Corporation, trade name: KJ4B-QA06NTB-STDV, piezo type, number of nozzles 2,656) in an environment with a temperature of 25 ⁇ 1 ° C and a relative humidity of 30 ⁇ 5% RH.
• the evaluation device manufactured by Tritec Co., Ltd. was filled with ink 1.
• the printing conditions are set to head voltage 26V, frequency 20kHz, ejection droplet amount 18pL, head temperature 32 ° C., resolution 600dpi, number of flushing before ejection 200, negative pressure 4.0kPa, and the longitudinal direction and transport direction of the base material are set.
• the base material was fixed to the transport table under reduced pressure in the same orientation. Under the same temperature and humidity environment as above, the printing command was transferred to the printing evaluation device, and printing was performed with 100% duty and a single pass to obtain a conductive member 1.
• a commercially available photographic glossy paper for inkjet manufactured by Seiko Epson Corporation, trade name: photo paper ⁇ glossy>, model number: KA4100PSKR was used.
• Example 2 each conductive member was obtained in the same manner except that the inks shown in Table 2 were used.
• Comparative Example 1-1 was obtained by printing under the same conditions as in Example 1 and then heating at 120 ° C. for 1 hour using a vacuum dryer (manufactured by Yamato Scientific Co., Ltd., model: DVS402). The conductive member 1-1 was subjected to evaluation.
• the room temperature sintering property, conductivity and bending resistance were evaluated by the methods shown below. The results are shown in Table 2.
• ⁇ Evaluation of room temperature sinterability> The conductive members obtained in Examples and Comparative Examples were used with a stainless steel razor (Feather Safety Razor Co., Ltd., 76 razors for normal use, blade thickness 76 ⁇ m) on the side opposite to the surface on which the conductive image was formed. Cut vertically from the surface of. Next, the cut surface was attached to an SEM sample table (Nisshin EM Co., Ltd., Type-T) with an aluminum base carbon double-sided tape for SEM (Nisshin EM Co., Ltd., catalog number 732), and a field emission scanning electron microscope (FE) was attached.
• SEM sample table Nishin EM Co., Ltd., Type-T
• FE field emission scanning electron microscope
• ⁇ Measurement of volume resistivity ⁇ v> The conductive members obtained in Examples and Comparative Examples were stored for 24 hours in an environment of a temperature of 25 ° C. and a relative humidity of 50% RH after printing.
• the conductive member after storage was cut into a size of 1 cm ⁇ 2 cm with the above stainless steel razor. Next, the cut sample was measured using a resistivity meter (main body: Lorresta-GP, four probe probe: PSP probe, all manufactured by Mitsubishi Chemical Analytech Co., Ltd.), and the conductivity was separately measured by the method shown below.
• the thickness t of the image was input to the above resistivity meter, and the volume resistivity was displayed.
• Measurement of conductive image thickness The conductive members obtained in Examples and Comparative Examples were stored for 1 hour in an environment of a temperature of 25 ° C. and a relative humidity of 50% RH after printing. The conductive member after storage was observed using a field emission scanning electron microscope in the same manner as described above to obtain a secondary electron image. The coating film thickness was measured at 10 points of the conductive image in the secondary electron image, and the thickness t of the conductive image was obtained by arithmetic mean.
• ⁇ Bending resistance> The conductive members obtained in Examples and Comparative Examples were wound along a polystyrene rod having a diameter of 5 mm, and kept as it was in an environment of a temperature of 25 ° C. and a relative humidity of 50% RH for 1 hour. After that, it was opened again, the surface of the conductive image was wiped off with a soft cloth, and then the presence or absence of image defects was confirmed.
• the maximum length (mm) of the image defect was measured as an index of the bending resistance of the conductive member.
• the maximum length of the image defect was set to 0 mm. The smaller the maximum length of the image defect, the better the bending resistance of the conductive member.
• the conductive members of Examples 1 to 5 have room temperature sintering property, and are excellent in conductivity and bending resistance as compared with Comparative Examples 1-1, 1-2 and Comparative Example 2. Understand. On the other hand, it can be seen that Comparative Examples 1-1 and 1-2 do not have room temperature sinterability because dextrin is used as a dispersant. Further, in Comparative Example 1-1, after forming the conductive member in a normal temperature environment, the conductive member was further heated at 120 ° C. for 1 hour, but as compared with Examples 1 to 5, the conductivity and bending resistance were increased. It turns out that both are inferior. Since Comparative Example 2 uses succinic acid as a dispersant, it can be seen that although it has normal temperature sinterability, it is inferior in both conductivity and bending resistance as compared with Examples 1 to 5.

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• 2019
  • 2019-04-26 KR KR1020217034000A patent/KR20210140751A/ko not_active Withdrawn
  • 2019-04-26 EP EP19925778.3A patent/EP3961655A4/en active Pending
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  • 2019-04-26 US US17/605,923 patent/US12305055B2/en active Active
  • 2019-04-26 CN CN201980095770.XA patent/CN113728401B/zh active Active

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