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
  • C09D11/30—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
  • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
• • 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
• • 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

Definitions

• the present invention relates to a method for producing an ink containing metal fine particles, an ink containing metal fine particles, an ink for inkjet printing, and a method for producing a printed matter.
• metal fine particles are expected to be used in a wide variety of industrial applications due to the diversity of their functions.
• a wiring forming technique using metal fine particles as a conductive material for printed electronics is being studied.
• Patent Document 1 discloses a thickening agent for the purpose of providing a method for producing a highly conductive coating or pattern from a metal nanoparticle dispersion under moderate curing conditions. , metal nanoparticle dispersions comprising one or more additives selected from high-boiling solvents and wetting agents.
• JP-T-2015-522713 discloses that the dispersion medium contains a solvent having a specific amide structure for the purpose of obtaining a stable metallic nanoparticle dispersion system without the need for a polymer dispersant.
• Metallic nanoparticle dispersions and the like are described. Japanese National Publication of International Patent Application No.
• Patent Document 3 describes aggregation of metal nanoparticles suitable for the production of highly concentrated aqueous solutions of metal nanoparticles, especially silver nanoparticles, platinum nanoparticles and palladium nanoparticles.
• Metal nanoparticles stabilized with derivatized polyethyleneimine or polyvinylamine have been described with the aim of providing a method for producing metal nanoparticles that does not cause
• the present invention comprises a step 1 of mixing a metal oxide A, a polymer B, formic acid and a solvent C to obtain a mixture 1; a step 2 of heating the mixed solution 1 to obtain a fine metal particle dispersion; a step 3 of obtaining an ink containing metal fine particles by mixing the fine metal particle dispersion and formic acid;
• the polymer B contains a structural unit derived from a monomer (b-1) having a carboxy group and a structural unit derived from a monomer (b-2) having a polyoxyalkylene group
• the solvent C contains at least one selected from the group consisting of water, aliphatic monoalcohols having 1 to 4 carbon atoms and ketones having 3 to 4 carbon atoms,
• the content of the metal constituting the metal oxide A in the mixed liquid 1 is 28% by mass or more and 57% by mass or less, The mass ratio [polymer B/(polymer B+metal)] of the content of the polymer B to the total amount of the content
• Patent Literature 1 requires a refining step for replacing the solvent after manufacturing the fine metal particles, and cannot meet the demand for productivity.
• the technique of Patent Document 2 does not use a polymer dispersant, so it cannot provide a high degree of dispersion stability, and does not meet the performance requirements for inkjet printing.
• Patent Document 3 since fine metal particles are produced under excessively high-concentration conditions, coarse particles are generated, resulting in a decrease in conductivity.
• inks containing fine metal particles used for printing are required to have further improvements in productivity, conductivity, and ejection properties.
• the present invention provides a method for producing an ink containing fine metal particles that can be easily replaced with any solvent or does not require replacement of the solvent and has improved conductivity and ejection properties, an ink containing fine metal particles that has improved conductivity and ejection properties, and and a method for producing an inkjet printing ink and a printed matter using the ink containing metal fine particles.
• the present inventors have found that in a method for producing an ink containing metal fine particles, a liquid mixture containing a metal oxide, a polymer having a specific functional group, formic acid, and a solvent having a specific chemical structure is used to prepare a metal fine particle dispersion.
• the content of the metal constituting the metal oxide and the mass ratio of the content of the polymer to the total amount of the content of the metal constituting the polymer and the metal oxide are each set within a predetermined range Furthermore, by having a step of mixing formic acid with the obtained metal fine particle dispersion, the generation of coarse particles and particle aggregates can be suppressed, and the conductivity of the obtained metal fine particle-containing ink can be improved. I paid attention.
• the polymer B contains a structural unit derived from a monomer (b-1) having a carboxy group and a structural unit derived from a monomer (b-2) having a polyoxyalkylene group
• the solvent C contains at least one selected from the group consisting of water, aliphatic monoalcohols having 1 to 4 carbon atoms and ketones having 3 to 4 carbon atoms,
• the content of the metal constituting the metal oxide A in the mixed liquid 1 is 28% by mass or more and 57% by mass or less,
• the polymer B contains a structural unit derived from a monomer (b-1) having a carboxy group and a structural unit derived from a monomer (b-2) having a polyoxyalkylene group
• the solvent C contains at least one selected from the group consisting of water, aliphatic monoalcohols having 1 to 4 carbon atoms and ketones having 3 to 4 carbon atoms
• the content of the metal fine particles a is 8% by mass or more and 17% by mass or less
• the mass ratio of the content of the polymer B to the total amount of the content of the polymer B and the content of the metal fine particles a [polymer B/(polymer B + metal fine particles a)] is 0.05 or more and 0.17 or less.
• an ink containing fine metal particles an ink containing fine metal particles.
• At least one ink selected from the group consisting of the metal fine particle-containing ink described in [2] above and the inkjet printing ink described in [3] above is applied onto a substrate to form a metal film.
• a method for producing a printed matter comprising a step 5 of obtaining a printed matter.
• the method for producing an ink containing fine metal particles of the present invention includes Step 1 (hereinafter also simply referred to as “Step 1”) to obtain a mixed liquid 1 by mixing a metal oxide A, a polymer B, formic acid and a solvent C, and Step 2 (hereinafter also simply referred to as “step 2”) of heating step 1 to obtain a metal fine particle dispersion liquid (hereinafter simply referred to as “step 2”), and step 3 (hereinafter simply referred to as “step 3”), and the polymer B contains a structural unit derived from a monomer (b-1) having a carboxy group and a monomer (b-2) having a polyoxyalkylene group, and a solvent C Contains at least one selected from the group consisting of water, aliphatic monoalcohols having 1 to 4 carbon atoms and ketones having 3 to 4 carbon atoms, and metal oxide A in the mixed liquid 1 Containing metals is 28% by
• the metal fine particle-containing ink obtained by the production method according to the present invention is obtained by dispersing the metal fine particles a in a medium.
• the form of the fine metal particles a is not particularly limited as long as the particles are formed of at least the fine metal particles and the polymer B.
• a particle form in which the metal fine particles are encapsulated in the polymer B, a particle form in which the metal fine particles are uniformly dispersed in the polymer B, and a particle form in which the metal fine particles are exposed on the particle surface of the polymer B are included. Mixtures are also included.
• an ink containing fine metal particles with improved electrical conductivity and jettability which can easily be replaced with any solvent or does not require solvent replacement.
• the reason is not clear, it is considered as follows.
• the content of the metal constituting the metal oxide A in the mixed liquid 1 to 28% by mass or more it is possible to suppress the generation of coarse metal particles during the synthesis of the metal fine particles a.
• the mass ratio [polymer B/(polymer B+metal)] of the content of polymer B to the total amount of the content of polymer B and the content of metals constituting metal oxide A in mixed liquid 1 is 0.05.
• the amount of polymer B not adsorbed to the metal fine particles a can be reduced, and as a result, the conductivity and the ejection property are improved. It is considered possible.
• the solvent C containing at least one selected from the group consisting of water, aliphatic monoalcohols having 1 to 4 carbon atoms and ketones having 3 to 4 carbon atoms has a low boiling point, it is excellent in quick drying, Easy to replace with any solvent or no solvent replacement required.
• the formic acid mixed in step 3 promotes detachment of the polymer B from the surface of the metal fine particles, and the reducing action of the formic acid suppresses the oxidation of the metal fine particle surface, thereby promoting the sintering of the metal fine particles. It is believed that a metal film can be formed and good conductivity of the metal film can be maintained. For the above reasons, it is believed that, according to the production method of the present invention, it is possible to obtain an ink containing fine metal particles with improved conductivity and jettability, which can easily be replaced with any solvent or does not require solvent replacement. be done.
• Step 1 is a step of mixing metal oxide A, polymer B, formic acid and solvent C to obtain mixed solution 1 .
• the metal oxide A is reduced with formic acid, and it is believed that the metal fine particles a dispersed with the polymer B are formed.
• Metals (metal atoms) constituting metal oxide A include Group 4 transition metals such as titanium and zirconium; Group 5 transition metals such as vanadium and niobium; and Group 6 transition metals such as chromium, molybdenum and tungsten.
• Group 7 transition metals such as manganese, technetium and rhenium; Group 8 transition metals such as iron and ruthenium; Group 9 transition metals such as cobalt, rhodium and iridium; Group 10 transition metals, Group 11 transition metals such as copper, silver, and gold, Group 12 transition metals such as zinc and cadmium, Group 13 metals such as aluminum, gallium, and indium, germanium, tin, and lead.
• Group 14 metals such as One of the metals constituting the metal oxide A may be used as a single metal, or two or more of them may be used in combination as an alloy. Moreover, the metal oxide A can be used individually by 1 type or in mixture of 2 or more types.
• the metal oxide A preferably contains an oxide of a transition metal of Groups 4 to 11 and of Periods 4 to 6, more preferably copper, Including noble metal oxides such as nickel, gold, silver, platinum and palladium, more preferably including at least one oxide selected from gold, silver, copper, nickel and palladium, more preferably gold oxide and silver oxide and copper oxide, more preferably at least one selected from silver oxide and copper oxide, more preferably silver oxide, still more preferably silver oxide.
• the type of metal can be confirmed by high frequency inductively coupled plasma emission spectrometry.
• the content of silver oxide in the metal oxide A is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 98% by mass or more, more preferably substantially 100% by mass.
• substantially 100% by mass means that unintentionally contained components may be included. Components that are unintentionally included include, for example, unavoidable impurities.
• Polymer B has a structural unit derived from the monomer (b-1) having a carboxy group and a polyoxyalkylene group from the viewpoint of improving the dispersion stability of the ink containing fine metal particles and improving the conductivity and ejection properties. It contains structural units derived from the monomer (b-2).
• Examples of the basic structure of the polymer B include vinyl polymers such as acrylic resins, styrene resins, styrene-acrylic resins and acrylic silicone resins; condensation polymers such as polyesters and polyurethanes. Among them, vinyl-based polymers are preferable from the viewpoint of improving conductivity and ejection properties.
• Polymer B has a structural unit derived from the monomer (b-1) having a carboxy group and a polyoxyalkylene group from the viewpoint of improving the dispersion stability of the ink containing fine metal particles and improving the conductivity and ejection properties.
• a vinyl polymer containing a structural unit derived from the monomer (b-2) is preferred.
• Polymer B can be obtained by copolymerizing raw material monomers including monomer (b-1) and monomer (b-2).
• the vinyl-based polymer may be a block copolymer, a random copolymer, or an alternating copolymer.
• Monomer (b-1) having a carboxy group includes unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid and 2-methacryloyloxymethylsuccinic acid; unsaturated dicarboxylic acids such as maleic acid, itaconic acid, fumaric acid and citraconic acid. etc.
• the unsaturated dicarboxylic acid may be an anhydride.
• 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 dispersion stability of the ink containing fine metal particles and improving the conductivity and jettability.
• (meth)acrylic acid means at least one selected from acrylic acid and methacrylic acid.
• (Meth)acrylic acid” below has the same meaning.
• a monomer capable of introducing a polyalkylene glycol segment as a side chain of the polymer B is used from the viewpoint of improving the dispersion stability of the metal fine particle-containing ink and improving the conductivity and ejection properties.
• the monomer include polyalkylene glycol (meth)acrylates, alkoxypolyalkylene glycol (meth)acrylates, phenoxypolyalkylene glycol (meth)acrylates, and the like.
• the monomer (b-2) may be used alone or in combination of two or more.
• “(meth)acrylate” is at least one selected from acrylate and methacrylate.
• “(Meth)acrylate” below has the same meaning.
• Monomer (b-2) is preferably polyalkylene glycol (meth)acrylate and alkoxypolyalkylene glycol (meth) from the viewpoint of improving the dispersion stability of the ink containing fine metal particles and improving conductivity and jettability. It is at least one selected from acrylates, and more preferably alkoxypolyalkylene glycol (meth)acrylate.
• the number of carbon atoms in the alkoxy group of the alkoxypolyalkylene glycol (meth)acrylate is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, from the same viewpoint as described above.
• alkoxy polyalkylene glycol (meth)acrylates examples include methoxy polyalkylene glycol (meth) acrylate, ethoxy polyalkylene glycol (meth) acrylate, propoxy polyalkylene glycol (meth) acrylate, butoxy polyalkylene glycol (meth) acrylate, octoxy Polyalkylene glycol (meth)acrylate and the like are included.
• the polyoxyalkylene group of the monomer (b-2) is preferably derived from an alkylene oxide having 2 or more and 4 or less carbon atoms from the viewpoint of improving the dispersion stability of the ink containing fine metal particles and improving the conductivity and jettability. Including units.
• the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide, preferably one or more selected from ethylene oxide and propylene oxide, and more preferably ethylene oxide.
• the number of alkylene oxide-derived units in the polyoxyalkylene group is preferably 2 or more, more preferably 3 or more, from the viewpoint of improving the dispersion stability of the ink containing fine metal particles and improving the conductivity and ejection properties.
• the polyoxyalkylene group is a copolymer containing an ethylene oxide-derived unit and a propylene oxide-derived unit from the viewpoint of improving the dispersion stability of the ink containing fine metal particles and improving the conductivity and jettability. is preferred.
• the molar ratio [EO/PO] between ethylene oxide units (EO) and 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, still more preferably 80/20 or less.
• a copolymer containing ethylene oxide-derived units and propylene oxide-derived units may be a block copolymer, a random copolymer, or an alternating copolymer.
• NK Ester AM-90G examples include NK Ester AM-90G, NK Ester AM-130G, NK Ester AM-230G, AMP-20GY and M-20G manufactured by Shin-Nakamura Chemical Co., Ltd. , M-40G, M-90G, M-230G, etc.; NOF CORPORATION's Blenmer PE-90, PE-200, PE-350, PME-100, PME-200, PME- 400, PME-1000, PME-4000, PP-500, PP-800, PP-1000, AP-150, AP-400, AP-550, 50PEP-300, 50POEP- 800B, 43PAPE-600B and the like.
• Polymer B preferably further contains a structural unit derived from the hydrophobic monomer (b-3) from the viewpoint of improving conductivity and ejection properties.
• hydrophobic monomer means that the amount of the monomer dissolved in 100 g of deionized water at 25° C. until saturation is less than 10 g.
• the dissolved amount of the monomer (b-3) is preferably 5 g or less, more preferably 1 g or less, from the viewpoint of improving conductivity and ejection properties.
• the monomer (b-3) is preferably at least one selected from aromatic group-containing monomers and (meth)acrylates having a hydrocarbon group derived from an aliphatic alcohol.
• (meth)acrylate is at least one selected from acrylate and methacrylate.
• (Meth)acrylate” below has the same meaning.
• 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 hetero atom, from the viewpoint of improving conductivity and dischargeability. and more preferably one or more selected from styrene-based monomers and aromatic group-containing (meth)acrylates.
• the molecular weight of the aromatic group-containing monomer is preferably less than 500.
• Styrenic monomers include styrene, ⁇ -methylstyrene, 2-methylstyrene, 4-vinyltoluene (4-methylstyrene), divinylbenzene and the like. Alpha-methylstyrene is preferred.
• aromatic group-containing (meth)acrylate phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate and the like are preferable from the viewpoint of improving conductivity and dischargeability, and benzyl (meth)acrylate is preferable. more preferred.
• the (meth)acrylate having a hydrocarbon group derived from an aliphatic alcohol preferably has a hydrocarbon group derived from an aliphatic alcohol having 1 to 22 carbon atoms from the viewpoint of improving conductivity and ejection properties.
• Monomer (b-3) is preferably an aromatic group-containing monomer, more preferably a styrenic monomer, still more preferably styrene, ⁇ -methylstyrene, 2- It is at least one selected from methylstyrene and 4-vinyltoluene (4-methylstyrene), more preferably at least one selected from styrene and ⁇ -methylstyrene.
• the polymer B contains structural units derived from the monomer (b-1) and structural units derived from the monomer (b-2) and does not contain structural units derived from the monomer (b-3), the monomer ( The content of b-1) and (b-2) in the raw material monomer (content as an unneutralized amount; the same shall apply hereinafter) or the constituent units derived from the monomer (b-1) and (b-2) in polymer B ) is as follows from the viewpoint of improving conductivity and ejection properties.
• the content of the monomer (b-1) is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, still more preferably 50 mol% or more, More preferably 60 mol% or more, and preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less, still more preferably 75 mol% or less.
• the content of the monomer (b-2) is preferably 10 mol% or more, more preferably 15 mol% or more, still more preferably 20 mol% or more, still more preferably 25 mol% or more, and preferably 90 mol.
• the content molar ratio of the monomer (b-1) and the monomer (b-2) [monomer (b-1)/monomer (b-2)] is preferably 0.5 or more, more preferably 1.0 or more, and further It is preferably 1.5 or more, and is preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.5 or less, still more preferably 3.0 or less, still more preferably 2.5 or less. be.
• the content of the monomers (b-1) to (b-3) in the raw material monomers during the production of the polymer B (as the unneutralized amount The same shall apply hereinafter) or the content of structural units derived from the monomers (b-1) to (b-3) in the polymer B is as follows from the viewpoint of improving conductivity and ejection properties.
• 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 60 mol% or less, more preferably 50 mol%. % or less, more preferably 45 mol % or less.
• 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 25 mol%. % or less, more preferably 20 mol % or less.
• the content of the monomer (b-3) is preferably 30 mol% or more, more preferably 35 mol% or more, still more preferably 40 mol% or more, and preferably 90 mol% or less, more preferably 85 mol%. % or less, more preferably 80 mol % or less.
• the content molar ratio of the monomer (b-1) and the monomer (b-2) [monomer (b-1)/monomer (b-2)] is preferably 0.5 or more, more preferably 1 or more, and still more preferably It is 1.5 or more, and preferably 5 or less, more preferably 4 or less, and even more preferably 3.5 or less.
• the polymer B contains a structural unit derived from at least one selected from (meth)acrylic acid and maleic acid as the monomer (b-1) and an alkoxy as the monomer (b-2).
• a vinyl polymer containing a structural unit derived from polyalkylene glycol (meth)acrylate is preferable, and a structural unit derived from at least one selected from (meth)acrylic acid and maleic acid as the monomer (b-1), the monomer (b-2 ) as a structural unit derived from alkoxypolyalkylene glycol (meth) acrylate, and at least one selected from (meth) acrylate having a hydrocarbon group derived from a styrene monomer and an aliphatic alcohol as a monomer (b-3).
• Vinyl-based polymers containing units are more preferred.
• Polymer B may be synthesized by a known method, or may be a commercially available product. Commercially available products of Polymer B include DISPERBYK-
• the content of the vinyl-based polymer containing the structural unit derived from the monomer (b-1) having a carboxy group and the structural unit derived from the monomer (b-2) having a polyoxyalkylene group in the polymer B is the amount of the metal fine particle-containing ink. From the viewpoint of improving dispersion stability and improving conductivity and ejection properties, it is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 98% by mass or more. More preferably, it is substantially 100% by mass.
• “substantially 100% by mass” means that unintentionally contained components may be included.
• the unintentionally included component means that, for example, a polymer B component other than the vinyl-based polymer included in the vinyl-based polymer may be included.
• the content of the vinyl polymer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 90% by mass or more, from the viewpoint of improving the dispersion stability of the ink containing fine metal particles and improving the conductivity and dischargeability. 95% by mass or more, more preferably 98% by mass or more, more preferably substantially 100% by mass.
• substantially 100% by mass means that unintentionally contained components may be included.
• the unintentionally included component means that, for example, a polymer B component other than the vinyl-based polymer included in the vinyl-based polymer may be included.
• a structural unit derived from at least one selected from (meth)acrylic acid and maleic acid as the monomer (b-1) and a structural unit derived from an alkoxypolyalkylene glycol (meth)acrylate as the monomer (b-2) is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 90% by mass or more, from the viewpoint of improving the dispersion stability of the metal fine particle-containing ink and improving the conductivity and jettability. It is preferably 95% by mass or more, more preferably 98% by mass or more, and still more preferably substantially 100% by mass.
• substantially 100% by mass means that unintentionally contained components may be included.
• the unintentionally included component means that, for example, a polymer B component other than the vinyl-based polymer included in the vinyl-based polymer may be included.
• substantially 100% by mass means that unintentionally contained components may be included.
• the unintentionally included component means that, for example, a polymer B component other than the vinyl-based polymer included in the vinyl-based polymer may be included.
• the number-average molecular weight Mn of the polymer B is preferably 1,000 or more, more preferably 2,000 or more, and still more preferably 2,000 or more, from the viewpoint of improving the dispersion stability of the ink containing fine metal particles and improving the conductivity and jettability. is 3,000 or more, and is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 30,000 or less, even more preferably 10,000 or less.
• the number average molecular weight Mn is measured by the method described in Examples.
• the acid value of polymer B is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, and still more preferably 15 mgKOH, from the viewpoint of improving the dispersion stability of the ink containing fine metal particles and improving the conductivity and jettability. /g or more, and preferably 200 mgKOH/g or less, more preferably 120 mgKOH/g or less.
• the acid value of polymer B can be measured by the method described in Examples, but can also be calculated from the mass ratio of the constituent monomers.
• the mixed liquid 1 contains water, an aliphatic monoalcohol having 1 to 4 carbon atoms, and a It contains a solvent C containing at least one selected from the group consisting of ketones.
• Solvent C is preferably methanol, ethanol, n-propanol, isopropanol, isobutanol, n-butanol, acetone, or methyl ethyl ketone from the viewpoint of improving the dispersion stability of the ink containing fine metal particles and improving the conductivity and ejection properties.
• At least one selected from water more preferably at least one selected from ethanol, n-propanol, isopropanol, isobutanol, methyl ethyl ketone, and water, more preferably ethanol, n-propanol, isopropanol, It contains at least one selected from methyl ethyl ketone and water, more preferably at least one selected from ethanol and water, and still more preferably ethanol.
• the boiling point of Solvent C at 1 atm is preferably 50° C. or higher, more preferably 60° C. or higher, and even more preferably 70° C. or higher, from the viewpoint of improving the dispersion stability of the ink containing fine metal particles and improving the ejection properties. , more preferably 75 ° C. or higher, and from the viewpoint of improving quick-drying property, solvent substitution, and conductivity, preferably 120 ° C. or lower, more preferably 110 ° C. or lower, further preferably 105 ° C. or lower, further preferably 100 ° C. °C or less.
• the boiling point of the said solvent C is the weighted average value weighted by the content (mass %) of each solvent.
• Solvent C is at least one selected from the group consisting of water, aliphatic monoalcohols having 1 to 4 carbon atoms, and ketones having 3 to 4 carbon atoms (hereinafter also referred to as "solvent C1"). (Also referred to as “solvent C2”) may be contained, but the solvent C2 is included from the viewpoint of improving the dispersion stability of the metal fine particle-containing ink and improving the quick-drying property, solvent substitution property, conductivity, and ejection property. The amount is preferably such that the weighted average value of the boiling points of solvent C satisfies the above range of boiling points.
• the content of the solvent C2 in the mixed liquid 1 is preferably 5% by mass or less from the viewpoint of improving the dispersion stability of the ink containing fine metal particles and improving the quick-drying property, the solvent-substituting property, the conductivity, and the ejection property. More preferably 3% by mass or less, still more preferably 1% by mass or less, still more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less, still more preferably substantially 0% by mass.
• substantially 0% by mass means that unintended components may be included. Examples of components that are included unintentionally include solvent C2 included in solvent C1.
• the total content of water in solvent C, aliphatic monoalcohol having 1 to 4 carbon atoms, and ketone having 3 to 4 carbon atoms improves quick-drying, solvent substitution, conductivity and dischargeability. from the viewpoint of increasing the content of the % or more, more preferably substantially 100% by mass.
• substantially 100% by mass means that unintentionally contained components may be included. Examples of components that are unintentionally included include solvent C other than solvent C1 included in solvent C1.
• the total content of methanol, ethanol, n-propanol, isopropanol, isobutanol, n-butanol, acetone, methyl ethyl ketone, and water in solvent C should be , preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably 99% by mass or more, still more preferably 99.9% by mass or more, More preferably, it is substantially 100% by mass.
• substantially 100% by mass means that unintentionally contained components may be included. Examples of components that are unintentionally included include a solvent C other than the solvent contained in the solvent.
• the total content of ethanol, n-propanol, isopropanol, methyl ethyl ketone and water in solvent C is preferably 80% by mass or more, more preferably 90% by mass, from the viewpoint of improving quick-drying property, solvent substitution property, conductivity and ejection property.
• substantially 100% by mass means that unintentionally contained components may be included. Examples of components that are unintentionally included include a solvent C other than the solvent contained in the solvent.
• composition of mixed liquid 1 The content of the metal oxide A in the mixed liquid 1 is preferably 30% by mass or more, more preferably 33% by mass or more, and still more preferably 35% by mass or more, from the viewpoint of improving conductivity and dischargeability.
• the content is preferably 62% by mass or less, more preferably 60% by mass or less, and even more preferably 59% by mass or less.
• the content of the polymer B in the mixed liquid 1 is preferably 2.0% by mass or more, more preferably 2.5% by mass or more, and still more preferably 2.8% by mass, from the viewpoint of improving conductivity and ejection properties.
• the content of formic acid in the mixed liquid 1 is preferably 5.0% by mass or more, more preferably 5.5% by mass or more, and still more preferably 6.0% by mass or more, from the viewpoint of improving conductivity and ejection properties. and is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 9.5% by mass or less.
• the content of the solvent C in the mixed liquid 1 is preferably 12% by mass or more, more preferably 15% by mass or more, and still more preferably 17% by mass or more, from the viewpoint of improving conductivity and ejection properties, and It is preferably 50% by mass or less, more preferably 47% by mass or less, and even more preferably 44% by mass or less.
• the content of the metals constituting the metal oxide A in the mixed liquid 1 is 28% by mass or more, preferably 32% by mass or more, more preferably 37% by mass or more, and further It is preferably 40% by mass or more, and 57% by mass or less, preferably 55% by mass or less, more preferably 51% by mass or less, and even more preferably 45% by mass or less.
• the ratio of the content of polymer B to the total amount of the content of polymer B and the content of metals constituting metal oxide A in mixed liquid 1 [polymer B / (polymer B + metal)] is the conductivity and ejection property is 0.05 or more, preferably 0.055 or more, more preferably 0.06 or more from the viewpoint of improving the is 0.13 or less, more preferably 0.12 or less.
• the molar ratio [formic acid/metal] of the content of formic acid to the content of the metal constituting the metal oxide A in the mixed liquid 1 is preferably 0.05 or more, or more, from the viewpoint of improving the conductivity and the ejection property. preferably 0.13 or more, more preferably 0.20 or more, still more preferably 0.30 or more, still more preferably 0.35 or more, and preferably 1.00 or less, more preferably 0.80 or less, It is more preferably 0.70 or less, still more preferably 0.60 or less, and even more preferably 0.50 or less.
• the content of the metal oxide A is preferably 30% by mass or more and 62% by mass or less, and the content of the polymer B is preferably 2.0% by mass or more and 10% by mass, from the viewpoint of improving conductivity and dischargeability.
• % by mass or less the content of formic acid is preferably 5.0% by mass or more and 15% by mass or less, and the content of solvent C is preferably 12% by mass or more and 50% by mass or less.
• metal oxide A, polymer B, formic acid and solvent C can be mixed by a known method, and from the viewpoint of improving productivity, a mixed solution containing metal oxide A, polymer B and solvent C is prepared in advance.
• a method of adding and mixing formic acid after obtaining is preferred.
• the mixing temperature in step 1 is preferably ⁇ 10° C. or higher, more preferably 0° C. or higher, still more preferably 10° C. or higher, still more preferably 15° C. or higher, and still more preferably 20° C. or higher.
• the temperature is preferably 45° C. or lower, more preferably 40° C. or lower, even more preferably 35° C. or lower, still more preferably 30° C. or lower, from the viewpoint of improving the uniformity, conductivity and dischargeability of the fine metal particles.
• the stirring speed in step 1 is preferably 1 m/s or more, more preferably 2 m/s or more, and still more preferably 4 m/s or more, from the viewpoint of improving the uniformity, conductivity, and dischargeability of the metal fine particles. From the viewpoint of improving properties, it is preferably 21 m/s or less, more preferably 13 m/s or less, and even more preferably 8 m/s or less.
• the mixing time in step 1 is preferably 2 minutes or more, more preferably 5 minutes or more, from the viewpoint of improving the uniformity, conductivity, and dischargeability of the metal fine particles, and preferably 60 minutes from the viewpoint of improving productivity. minutes or less, more preferably 45 minutes or less, and even more preferably 35 minutes or less.
• Step 2 is a step of heating the mixture 1 obtained in Step 1 to obtain a fine metal particle dispersion.
• the heating temperature in step 2 is preferably 40° C. or higher, more preferably 50° C. or higher, and still more preferably 55° C. or higher, from the viewpoint of improving productivity, uniformity of fine metal particles, conductivity, and dischargeability. From the viewpoint of improving properties, the temperature is preferably 120° C. or lower, more preferably 100° C. or lower, still more preferably 80° C. or lower, and even more preferably 70° C. or lower.
• the stirring speed in step 2 is preferably 1 m/s or more, more preferably 2 m/s or more, and still more preferably 4 m/s or more, from the viewpoint of improving the uniformity, conductivity, and dischargeability of the metal fine particles. From the viewpoint of improving properties, it is preferably 21 m/s or less, more preferably 13 m/s or less, and even more preferably 8 m/s or less.
• the heating time in step 2 is preferably 45 minutes or more, more preferably 60 minutes or more, and still more preferably 90 minutes or more, from the viewpoint of improving the uniformity, conductivity, and dischargeability of the metal fine particles, thereby improving productivity. From the viewpoint of increasing the temperature, the time is preferably 420 minutes or less, more preferably 300 minutes or less, and still more preferably 150 minutes or less.
• Step 3 the fine metal particle dispersion liquid obtained in step 2 is mixed with formic acid to obtain an ink containing fine metal particles.
• the mixing temperature in step 3 is preferably ⁇ 10° C. or higher, more preferably 0° C. or higher, still more preferably 10° C. or higher, still more preferably 15° C. or higher, and still more preferably 20° C. or higher.
• the temperature is preferably 45° C. or lower, more preferably 40° C. or lower, even more preferably 35° C. or lower, still more preferably 30° C. or lower, from the viewpoint of improving the uniformity, conductivity and dischargeability of the fine metal particles.
• the stirring speed in step 3 is preferably 0.05 m/s or more, more preferably 0.1 m/s or more, and still more preferably 0.05 m/s or more, from the viewpoint of improving the uniformity, conductivity, and ejection properties of the fine metal particle-containing ink. It is 2 m/s or more, and from the viewpoint of improving productivity, it is preferably 2 m/s or less, more preferably 1 m/s or less, and even more preferably 0.5 m/s or less.
• the mixing time in step 3 is preferably 5 minutes or longer, more preferably 15 minutes or longer, from the viewpoint of improving the uniformity, conductivity, and ejection properties of the ink containing fine metal particles, and is preferably from the viewpoint of improving productivity. is 90 minutes or less, more preferably 75 minutes or less, even more preferably 60 minutes or less, still more preferably 45 minutes or less.
• the amount of formic acid mixed in step 3 is preferably 0.8% by mass or more, more preferably 0.8% by mass or more, more preferably 0.8% by mass or more, from the viewpoint of improving conductivity, when the total amount of the fine metal particle-containing ink obtained in step 3 is taken as 100% by mass. 9% by mass or more, preferably 15% by mass or less, more preferably 12% by mass or less, even more preferably 10% by mass or less, even more preferably 9% by mass or less, and even more preferably 8% by mass, from the viewpoint of improving ejection properties % by mass or less, more preferably 7.5% by mass or less.
• the ink containing fine metal particles of the present invention contains fine metal particles a dispersed in a polymer B, formic acid, and a solvent C. containing structural units derived from the monomer (b-2) having, solvent C is water, at least one selected from the group consisting of aliphatic monoalcohols having 1 to 4 carbon atoms and ketones having 3 to 4 carbon atoms , the content of the metal fine particles a is 8% by mass or more and 17% by mass or less, and the mass ratio of the content of the polymer B to the total amount of the content of the polymer B and the content of the metal fine particles a [polymer B / (polymer B + The fine metal particles a)] is 0.05 or more and 0.17 or less.
• the metal fine particle-containing ink of the present invention can be obtained, for example, by the method for producing the metal fine particle-containing ink according to the present invention described above.
• the ink containing fine metal particles according to the present invention is obtained by dispersing fine metal particles a in a medium.
• the form of the fine metal particles a is not particularly limited as long as the particles are formed of at least the fine metal particles and the polymer B.
• a particle form in which the metal fine particles are encapsulated in the polymer B, a particle form in which the metal fine particles are uniformly dispersed in the polymer B, and a particle form in which the metal fine particles are exposed on the particle surface of the polymer B are included. Mixtures are also included.
• the ink containing fine metal particles According to the ink containing fine metal particles according to the present invention, it is possible to easily replace the solvent with any solvent, or it is not necessary to replace the solvent, and it is possible to improve the conductivity and the ejection property. Although the reason is not clear, it is considered as follows. First, by setting the content of the metal fine particles a to 17% by mass or less, it is possible to suppress the generation of aggregates of the metal fine particles a, and as a result, it is thought that the conductivity and the ejection property can be improved. Furthermore, by setting the content of the metal fine particles a to 8% by mass or more, it is possible to suppress the generation of coarse particles of the metal fine particles a, and as a result, it is thought that the conductivity and the ejection property can be improved.
• the mass ratio of the content of polymer B to the total content of polymer B and the content of metal fine particles a [polymer B/(polymer B + metal)] to 0.05 or more, the amount of polymer B can be sufficiently ensured, and as a result, the dispersion stability of the metal fine particles a can be improved to improve the ejection property, and the sufficient dispersion stability makes the printed coating uniform and improves the conductivity. It is thought that it is possible to Furthermore, by setting the [polymer B/(polymer B + metal)] to 0.17 or less, the amount of polymer B not adsorbed to the metal fine particles a can be reduced, and as a result, the conductivity and the ejection property are improved. It is considered possible.
• the solvent C containing at least one selected from the group consisting of water, aliphatic monoalcohols having 1 to 4 carbon atoms and ketones having 3 to 4 carbon atoms has a low boiling point, it is excellent in quick drying, Easy to replace with any solvent or no solvent replacement required.
• the ink containing fine metal particles contains formic acid, detachment of the polymer B from the surface of the fine metal particles is promoted, and oxidation of the fine metal particle surfaces is suppressed by the reducing action of formic acid, and sintering of the fine metal particles proceeds. do. As a result, it is considered that the printed coating film becomes more uniform and the conductivity can be further improved.
• the ink containing fine metal particles according to the present invention can be easily replaced with any solvent or does not require solvent replacement, and can improve conductivity and ejection properties.
• Metals (metal atoms) constituting the metal fine particles a include Group 4 transition metals such as titanium and zirconium; Group 5 transition metals such as vanadium and niobium; and Group 6 transition metals such as chromium, molybdenum and tungsten.
• Group 7 transition metals such as manganese, technetium, and rhenium
• Group 8 transition metals such as iron and ruthenium
• Group 9 transition metals such as cobalt, rhodium and iridium
• Group 11 transition metals such as copper, silver and gold
• Group 12 transition metals such as zinc and cadmium
• Group 13 metals such as aluminum, gallium and indium
• the group 14 metals of One of the metals constituting the fine metal particles a may be used as a single metal, or two or more of them may be used in combination as an alloy.
• fine-particles a can be used individually by 1 type or in mixture of 2 or more types.
• the metal constituting the fine metal particles a preferably contains transition metals of Groups 4 to 11 and Periods 4 to 6, more preferably copper, from the viewpoint of improving conductivity and dischargeability.
• Including noble metals such as nickel, gold, silver, platinum and palladium, more preferably at least one selected from gold, silver, copper, nickel and palladium, more preferably at least one selected from gold, silver and copper more preferably at least one selected from silver and copper, more preferably silver, still more preferably silver.
• the type of metal can be confirmed by high frequency inductively coupled plasma emission spectrometry.
• the content of the metal in the fine metal particles a is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably 98% by mass, from the viewpoint of improving conductivity and ejection properties. % or more, more preferably substantially 100% by mass.
• the content of silver in the fine metal particles a is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 98% by mass, from the viewpoint of improving conductivity and ejection properties. % or more, more preferably substantially 100% by mass.
• substantially 100% by mass means that unintentionally contained components may be included. Components that are unintentionally included include, for example, unavoidable impurities.
• Polymer B used in the ink containing fine metal particles of the present invention are the same as those of the polymer B used in the method for producing the ink containing fine metal particles according to the present invention described above.
• a preferred embodiment of the solvent C used in the ink containing metal microparticles of the present invention is the same as the solvent C used in the method for producing the ink containing metal microparticles according to the present invention described above.
• the content of the metal fine particles a in the metal fine particle-containing ink according to the present invention is 8% by mass or more, preferably 10% by mass or more, more preferably 11.5% by mass or more, from the viewpoint of improving conductivity, From the viewpoint of improving ejection properties, it is 17% by mass or less, preferably 16.5% by mass or less.
• the content of the fine metal particles a in the fine metal particle-containing ink according to the present invention is 8% by mass or more and 17% by mass or less, preferably 10% by mass or more and 17% by mass or less, more preferably 11. It is 5 mass % or more and 17 mass % or less, more preferably 11.5 mass % or more and 16.5 mass % or less.
• the content of the polymer B in the metal fine particle-containing ink according to the present invention is preferably 0.7% by mass or more, more preferably 0.8% by mass or more, and still more preferably 0.9% by mass, from the viewpoint of improving ejection properties. % by mass or more, preferably 2.5% by mass or less, more preferably 2.3% by mass or less, even more preferably 2.1% by mass or less, still more preferably 1.9% by mass, from the viewpoint of improving conductivity % or less, more preferably 1.7 mass % or less. Taking these points together, the content of polymer B in the ink containing fine metal particles according to the present invention is preferably 0.7% by mass or more and 2.5% by mass or less, more preferably 0.7% by mass or more and 2.5% by mass or less.
• the content of formic acid in the metal fine particle-containing ink according to the present invention is preferably 0.8% by mass or more, more preferably 0.9% by mass or more, from the viewpoint of improving conductivity, and improves ejection properties. From the viewpoint, it is preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less, still more preferably 9% by mass or less, even more preferably 8% by mass or less, still more preferably 7.5% by mass. It is below. Taking these points together, the content of formic acid in the ink containing fine metal particles according to the present invention is preferably 0.8% by mass or more and 15% by mass or less, more preferably 0.8% by mass or more and 12% by mass or less.
• the content of the solvent C in the metal fine particle-containing ink according to the present invention is preferably 70% by mass or more, more preferably 72% by mass or more, still more preferably 73% by mass or more, and even more preferably, from the viewpoint of improving ejection properties. is 75% by mass or more, and from the viewpoint of improving conductivity, it is preferably 90% by mass or less, more preferably 88% by mass or less, and more preferably 86% by mass or less.
• the mass ratio [polymer B/(polymer B+metal)] of the content of polymer B to the total amount of the content of polymer B and the content of metal fine particles a in the ink containing fine metal particles according to the present invention improves the ejection property.
• the mass ratio of the content of polymer B to the total amount of the content of polymer B and the content of metal fine particles a in the ink containing fine metal particles according to the present invention is 0.05 or more and 0.17 or less, preferably 0.05 or more and 0.155 or less, more preferably 0.05 or more and 0.14 or less, still more preferably 0.05 or more and 0.125 or less, still more preferably It is 0.055 or more and 0.125 or less, more preferably 0.06 or more and 0.125 or less.
• the molar ratio [formic acid/metal] of the content of formic acid to the content of metal constituting the fine metal particles a in the fine metal particle-containing ink according to the present invention is preferably 0.1 or more from the viewpoint of improving conductivity. It is more preferably 0.12 or more, still more preferably 0.14 or more, still more preferably 0.16 or more, and from the viewpoint of improving ejection properties, it is preferably 2 or less, more preferably 1.9 or less, and still more preferably It is 1.6 or less, more preferably 1.4 or less, and even more preferably 1.3 or less.
• the molar ratio [formic acid/metal] of the content of formic acid to the content of metal constituting the fine metal particles a in the fine metal particle-containing ink according to the present invention is preferably 0.1 or more and 2 or less. , more preferably 0.1 or more and 1.9 or less, more preferably 0.12 or more and 1.6 or less, still more preferably 0.12 or more and 1.4 or less, still more preferably 0.12 or more and 1.3 or less, and further It is preferably 0.14 or more and 1.3 or less, more preferably 0.16 or more and 1.3 or less.
• the average particle size of the metal fine particles a in the metal fine particle-containing ink according to the present invention is preferably 3 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more, and still more preferably, from the viewpoint of improving conductivity and ejection properties. It is 30 nm or more, and preferably 100 nm or less, more preferably 90 nm or less, even more preferably 80 nm or less, still more preferably 70 nm or less.
• the average particle size of the fine metal particles a can be calculated by measuring the particle size by a dynamic light scattering method using a laser particle analysis system "ELS-8000" (manufactured by Otsuka Electronics Co., Ltd.) and by cumulant method analysis.
• the measurement conditions are a temperature of 25° C., an angle between the incident light and the detector of 90°, and the number of accumulations of 100 times.
• a sample was weighed into a screw tube (No. 5 manufactured by Maruem Co., Ltd.), water was added so that the solid content concentration was 5 ⁇ 10 ⁇ 3 mass %, and the mixture was stirred at 25° C. for 1 hour using a magnetic stirrer. can be used.
• the viscosity of the ink containing fine metal particles according to the present invention at 30° C. is preferably 1 mPa ⁇ s or more, more preferably 1.5 mPa ⁇ s or more, and still more preferably 1.8 mPa ⁇ s, from the viewpoint of improving conductivity and ejection properties.
• s or more and is preferably 60 mPa s or less, more preferably 50 mPa s or less, still more preferably 30 mPa s or less, still more preferably 10 mPa s or less, still more preferably 5 mPa s or less, still more preferably 3 mPa ⁇ It is less than or equal to s.
• the viscosity of the ink can be measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., model number: TV-25, using a standard cone rotor of 1°34′ ⁇ R24, rotation speed of 100 rpm).
• the pH at 20° C. of the ink containing fine metal particles according to the present invention is preferably 7.0 or higher, more preferably 7.2 or higher, and still more preferably 7.5 or higher, from the viewpoint of improving conductivity and ejection properties. , and is preferably 11 or less, more preferably 10 or less, and still more preferably 9.5 or less.
• the pH of the ink can be measured by a conventional method.
• the metal fine particle-containing ink according to the present invention can improve ejection properties and can form a metal film with improved conductivity, it is particularly suitable for inkjet printing, flexographic printing, gravure printing, screen printing, offset printing, and dispensers. It can be suitably used for various printing such as printing. Among others, the ink containing fine metal particles according to the present invention is preferably used for inkjet printing because it can improve the ejection property as described above.
• the metal fine particle-containing ink according to the present invention can be used in a wide range of applications because it can improve ejection properties and form a metal film with improved conductivity.
• Such uses include, for example, decorative materials that impart specular gloss; conductive materials such as wiring materials, electrode materials, and multilayer ceramic capacitors (hereinafter also referred to as “MLCC”) used for forming conductive circuits; solders, etc. various sensors; automatic recognition technology using short-range wireless communication (RFID (radio frequency identifier), hereinafter also referred to as "RFID”) antennas such as tags; catalysts; optical materials;
• RFID radio frequency identifier
• the ink containing fine metal particles according to the present invention is preferably used for producing a printed matter on which a conductive circuit is formed.
• the method for producing the ink for inkjet printing includes mixing the metal fine particle-containing ink according to the present invention, a surfactant, and, if necessary, a solvent, and performing inkjet printing. It is preferable to include a step 4 of obtaining ink for printing. That is, the inkjet printing ink according to the present invention contains the metal fine particle-containing ink and the surfactant according to the present invention.
• a nonionic surfactant is preferable and selected from acetylene glycol-based surfactants and silicone-based surfactants from the viewpoint of maintaining appropriate surface tension of the ink and improving wettability to the printing medium.
• One or more surfactants are more preferable, and it is even more preferable to use an acetylene glycol-based surfactant and a silicone-based surfactant in combination.
• acetylene glycol surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3, 5-dimethyl-1-hexyne-3-ol, 2,4-dimethyl-5-hexyne-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,5,8,11- acetylenic diols such as tetramethyl-6-dodecyne-5,8-diol, and their ethylene oxide adducts;
• silicone-based surfactants include dimethylpolysiloxane, polyether-modified silicone, amino-modified silicone, carboxy-modified silicone, and the like. From the same viewpoint as above, polyether-modified silicone is preferred.
• the solvent is preferably at least one selected from the group consisting of water, aliphatic monoalcohols having 1 to 4 carbon atoms, and ketones having 3 to 4 carbon atoms, from the viewpoint of improving conductivity and ejection properties.
• the solvent preferably contains at least one selected from methanol, ethanol, n-propanol, isopropanol, isobutanol, butanol, acetone, methyl ethyl ketone, and water, more preferably, from the viewpoint of improving conductivity and ejection properties.
• step 4 from the viewpoint of improving the uniformity, conductivity, and ejection properties of the fine metal particles, it is preferable to add and mix the surfactant and the solvent in this order with the ink containing the fine metal particles.
• the mixing temperature in step 4 is, for example, 20° C. or higher and 35° C. or lower. It is preferable to filter the ink for inkjet printing from the viewpoint of improving conductivity and ejection properties.
• composition of ink for inkjet printing The content of the surfactant in the ink for inkjet printing according to the present invention is preferably 0% by mass or more, more preferably 0.02% by mass or more, and still more preferably, from the viewpoint of improving droplet formation and wettability. is 0.05% by mass or more, and is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.3% by mass from the viewpoint of improving the uniformity, conductivity, and ejection properties of the metal fine particles. % by mass or less.
• the content of the metal fine particles a in the ink for inkjet printing according to the present invention is preferably 8% by mass or more, more preferably 10% by mass or more, and still more preferably 11.5% by mass or more, from the viewpoint of improving conductivity. , and from the viewpoint of improving ejection properties, it is preferably 17% by mass or less, more preferably 16.5% by mass or less.
• the content of the polymer B in the ink for inkjet printing according to the present invention is preferably 0.7% by mass or more, more preferably 0.8% by mass or more, and still more preferably 0.9% by mass, from the viewpoint of improving ejection properties.
• the content of formic acid in the ink for inkjet printing according to the present invention is preferably 0.8% by mass or more, more preferably 0.9% by mass or more, from the viewpoint of improving conductivity, and improves ejection properties. From the viewpoint, it is preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less, still more preferably 9% by mass or less, even more preferably 8% by mass or less, still more preferably 7.5% by mass.
• the content of the solvent C in the ink for inkjet printing according to the present invention is preferably 70% by mass or more, more preferably 72% by mass or more, still more preferably 73% by mass or more, and still more preferably, from the viewpoint of improving ejection properties. is 75% by mass or more, and from the viewpoint of improving conductivity, it is preferably 90% by mass or less, more preferably 88% by mass or less, and more preferably 86% by mass or less.
• the mass ratio [polymer B/(polymer B + metal)] of the content of polymer B to the total amount of the content of polymer B and the content of metal fine particles a in the ink for inkjet printing according to the present invention improves the ejection property.
• the ink of the present invention contains, as other components other than the above components, a fixing aid such as a dispersion of polymer particles, a humectant, a wetting agent, a penetrant, a viscosity modifier, and an eraser, as long as the effects of the present invention are not impaired.
• a fixing aid such as a dispersion of polymer particles, a humectant, a wetting agent, a penetrant, a viscosity modifier, and an eraser, as long as the effects of the present invention are not impaired.
• Various additives such as foaming agents, antiseptics, antifungal agents and antirust agents may be contained.
• the method for producing a printed matter according to the present invention includes an ink containing metal fine particles obtained by the method for producing an ink containing metal fine particles according to the present invention, and an ink for inkjet printing obtained by the method for producing an ink for ink jet printing according to the present invention.
• a method including step 5 of applying at least one type of ink selected from the group consisting of onto a substrate to obtain a printed matter on which a metal film is formed is preferred. As a result, it is possible to obtain a printed matter on which a metal film having excellent conductivity, specular gloss, etc. is formed.
• a patterned printed image can be formed on a substrate to form a patterned metal film, and the patterned metal film can be used as a conductive circuit. That is, it is preferable to use the method for producing a printed matter according to the present invention as a method for producing a printed matter in which a conductive circuit is formed on a substrate.
• the base material may be called a "substrate".
• Examples of the substrate include paper; fabric; resin; metal; glass; Examples of the paper substrate include coated paper (coated paper, art paper, etc.), uncoated paper, plain paper, kraft paper, synthetic paper, processed paper, cardboard, and the like.
• the fabric used as the base material includes fabrics made of natural fibers such as cotton, silk, and hemp, synthetic fibers such as rayon fibers, acetate fibers, nylon fibers, and polyester fibers, and blended fabrics made of two or more of these fibers. mentioned.
• resin substrates examples include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polypropylene (PP), polyamide (PA), polyimide (PI), polyvinyl chloride (PVC), poly Synthetic resin films such as methyl methacrylate (PMMA), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), and polycarbonate (PC) can be mentioned.
• metal substrates include substrates using metals such as gold, silver, copper, palladium, platinum, aluminum, nickel, and tin.
• the substrate is preferably at least one selected from paper substrates and resin substrates, more preferably paper substrates, from the viewpoint of bending resistance.
• the base material may be a rigid base material or a flexible base material, but the ink containing fine metal particles is a flexible base material from the viewpoint of forming a metal film having excellent bending resistance. is preferred.
• a method for printing the ink onto the substrate various patterning printing methods such as inkjet printing, flexographic printing, gravure printing, screen printing, offset printing, and dispenser printing are preferable, and inkjet printing is more preferable.
• a fine conductive circuit can be formed on the base material, and a design with excellent mirror surface design can be applied to the base material.
• the amount of the ink to be applied to the base material can be appropriately adjusted according to the size and type of the circuit or electrode to be formed, the degree of specular gloss desired, and the design.
• inkjet printing When the metal fine particle-containing ink according to the present invention is used for inkjet printing, and when the ink for inkjet printing is used, the ink is loaded into a known inkjet printing apparatus and ejected onto a substrate as ink droplets. A printed image can be formed. There are thermal type and piezo type ink jet printing devices, and the ink is more preferably used for thermal type ink jet printing.
• the head temperature of the inkjet head is preferably 15° C. or higher, more preferably 20° C. or higher, still more preferably 23° C. or higher, and is preferably 45° C. or lower, more preferably 40° C. or lower, further preferably 35° C. or lower. , and more preferably 30°C or less.
• the drive frequency of the head is preferably 1 kHz or higher, more preferably 5 kHz or higher, still more preferably 8 kHz or higher, and is preferably 50 kHz or lower, more preferably 40 kHz or lower, and still more preferably, from the viewpoint of printing efficiency. It is 20 kHz or less, more preferably 15 kHz or less.
• the ejected droplet volume of the ink according to the present invention is preferably 3 pL or more, more preferably 5 pL or more, and preferably 30 pL or less, more preferably 20 pL or less, and even more preferably 10 pL or less per droplet.
• the printing 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 700 dpi or less.
• “resolution” in this specification refers to the number of dots per inch (2.54 cm) formed on the substrate.
• resolution of 600 dpi means that when ink droplets are ejected onto a substrate using a line head in which the number of nozzle holes per length of the nozzle row is arranged at 600 dpi (dots/inch), 1 A row of dots of 600 dpi per inch is formed in a direction perpendicular to the transport direction of the substrate. It means that a line of dots of 600 dpi is formed.
• the resolution in the direction perpendicular to the conveying direction of the substrate and the resolution in the conveying direction are expressed as the same value.
• the temperature of the sintering treatment is preferably the temperature at which the base material is deformed, that is, below the heat-resistant temperature. Specifically, from the viewpoint of reducing the resistivity of the metal film, it is under normal pressure, preferably 25 ° C. or higher, more preferably 25 ° C. or higher. is 50°C or higher, more preferably 100°C or higher, more preferably 120°C or higher, still more preferably 140°C or higher, and preferably 200°C or lower, more preferably 180°C or lower, further preferably 160°C or lower. be.
• the relative humidity of the environment surrounding the sintering process is preferably 20% or higher, more preferably 30% or higher, and preferably 65% or lower, more preferably 60% or lower, and even more preferably 50% or lower.
• the sintering treatment is preferably carried out at a high temperature of 100° C. or higher and then stored at a low temperature.
• the low-temperature treatment is preferably performed by storing at room temperature (10° C. or higher and 35° C. or lower).
• the time of the high-temperature treatment in the sintering treatment can be appropriately adjusted depending on the temperature of the treatment. minutes or more, and from the viewpoint of productivity, the time is preferably 6 hours or less, more preferably 3 hours or less, even more preferably 1 hour or less, and even more preferably 30 minutes or less.
• the time of the low-temperature treatment in the sintering treatment can be appropriately adjusted depending on the temperature of the treatment.
• the sintering treatment may be performed under an air atmosphere or under an inert gas atmosphere such as nitrogen gas. is preferred.
• the method of the sintering treatment is not particularly limited.
• the printed matter obtained by the production method according to the present invention has good conductivity, so it can be used for various electronic and electrical devices as a conductive composite material including a substrate and a conductive circuit.
• the conductive composite material is an RFID tag; capacitors such as MLCC; LTCC substrate; electronic paper; liquid crystal display, organic EL display, image display device such as touch panel; organic EL element; wiring boards such as; organic solar cells; flexible batteries; and various devices such as sensors such as flexible sensors.
• Step 1 of mixing metal oxide A, polymer B, formic acid and solvent C to obtain mixed solution 1; a step 2 of heating the mixed solution 1 to obtain a fine metal particle dispersion; a step 3 of obtaining an ink containing metal fine particles by mixing the fine metal particle dispersion and formic acid;
• the polymer B contains a structural unit derived from a monomer (b-1) having a carboxy group and a structural unit derived from a monomer (b-2) having a polyoxyalkylene group
• the solvent C contains at least one selected from the group consisting of water, aliphatic monoalcohols having 1 to 4 carbon atoms and ketones having 3 to 4 carbon atoms,
• the content of the metal constituting the metal oxide A in the mixed liquid 1 is 28% by mass or more and 57% by mass or less, The mass ratio [polymer B/(polymer B+metal)] of the content of the polymer B
• Metal oxide A contains silver oxide
• the polymer B comprises a vinyl-based polymer containing a structural unit derived from a monomer (b-1) having a carboxy group and a structural unit derived from a monomer (b-2) having a polyoxyalkylene group
• the solvent C contains at least one selected from the group consisting of water, aliphatic monoalcohols having 1 to 4 carbon atoms and ketones having 3 to 4 carbon atoms,
• the content of the metal constituting the metal oxide A in the mixed liquid 1 is 28% by mass or more and 57% by mass or less, The mass ratio [polymer B/(polymer B+metal)] of the content of the polymer B to the total amount
• Metal oxide A contains silver oxide
• the polymer B contains structural units derived from the monomer (b-1) having a carboxy group, structural units derived from the monomer (b-2) having a polyoxyalkylene group, and structural units derived from the hydrophobic monomer (b-3).
• the solvent C contains at least one selected from the group consisting of water, aliphatic monoalcohols having 1 to 4 carbon atoms and ketones having 3 to 4 carbon atoms,
• the solvent C has a boiling point of 70° C. or higher and 105° C. or lower,
• the content of the metal constituting the metal oxide A in the mixed liquid 1 is 28% by mass or more and 57% by mass or less,
• the mass ratio [polymer B/(polymer B+metal)] of the content of the polymer B to the total amount of the content of the polymer B and the content of the metals constituting the metal oxide A in the mixed solution 1 is 0 0.05 or more and 0.15 or less, a method for producing an ink containing metal fine particles.
• the polymer B is a structural unit derived from at least one selected from (meth)acrylic acid and maleic acid as the monomer (b-1), and a structural unit derived from alkoxypolyalkylene glycol (meth)acrylate as the monomer (b-2).
• the method for producing an ink containing fine metal particles according to any one of ⁇ 1> to ⁇ 3>, which contains a vinyl polymer containing ⁇ 5>
• the polymer B has a structural unit derived from at least one selected from (meth)acrylic acid and maleic acid as the monomer (b-1), a structural unit derived from an alkoxypolyalkylene glycol (meth)acrylate as the monomer (b-2), And containing a structural unit derived from at least one selected from (meth) acrylate having a hydrocarbon group derived from styrenic monomers and aliphatic alcohols as the monomer (b-3), ⁇ 1> to any one of ⁇ 4>
• ⁇ 6> The metal according to any one of ⁇ 1> to ⁇ 5>, wherein the solvent C contains at least one selected from methanol, ethanol, n-propanol, isopropanol, isobutanol, n-butanol, acetone, methyl ethyl ketone, and water.
• a method for producing an ink containing fine particles A method for producing an ink containing fine particles.
• the solvent C contains at least one selected from ethanol, n-propanol, isopropanol, methyl ethyl ketone and water.
• the content of metal oxide A is 30% by mass or more and 62% by mass or less
• the content of polymer B is 2.0% by mass or more and 10% by mass or less
• the content of formic acid is 5.0% by mass.
• Any of ⁇ 1> to ⁇ 8>, wherein the molar ratio of the content of formic acid to the content of the metal constituting the metal oxide A in the mixed solution 1 [formic acid/metal] is 0.05 or more and 1.00 or less. 2.
• ⁇ 10> The method for producing an ink containing fine metal particles according to any one of ⁇ 2> to ⁇ 9>, wherein the content of silver oxide in metal oxide A is 80% by mass or more.
• the content of the vinyl polymer containing the structural unit derived from the monomer (b-1) having a carboxy group and the structural unit derived from the monomer (b-2) having a polyoxyalkylene group in the polymer B is 80% by mass or more.
• the structural unit derived from the monomer (b-1) having a carboxy group the structural unit derived from the monomer (b-2) having a polyoxyalkylene group and the structural unit derived from the hydrophobic monomer (b-3)
• a structural unit derived from at least one selected from (meth)acrylic acid and maleic acid as the monomer (b-1) and a structural unit derived from an alkoxypolyalkylene glycol (meth)acrylate as the monomer (b-2) The method for producing an ink containing fine metal particles according to any one of ⁇ 4> to ⁇ 12>, wherein the content of the vinyl polymer containing is 80% by mass or more.
• the content of a vinyl polymer containing a structural unit derived from at least one selected from styrene monomers and (meth)acrylates having a hydrocarbon group derived from an aliphatic alcohol as the monomer (b-3) is 80% by mass or more.
• ⁇ 15> Any one of ⁇ 1> to ⁇ 14>, wherein the total content of water in solvent C, aliphatic monoalcohol having 1 to 4 carbon atoms and ketone having 3 to 4 carbon atoms is 80% by mass or more.
• a method for producing an ink containing fine metal particles Any of ⁇ 6> to ⁇ 15>, wherein the total content of methanol, ethanol, n-propanol, isopropanol, isobutanol, n-butanol, acetone, methyl ethyl ketone, and water in solvent C is 80% by mass or more
• ⁇ 17> The method for producing an ink containing fine metal particles according to any one of ⁇ 7> to ⁇ 16>, wherein the total content of ethanol, n-propanol, isopropanol, methyl ethyl ketone and water in solvent C is 80% by mass or more.
• ⁇ 18> The method for producing an ink containing metal fine particles according to any one of ⁇ 1> to ⁇ 17>, wherein the content of the formic acid in the ink containing metal fine particles is 0.8% by mass or more and 15% by mass or less.
• the polymer B contains a structural unit derived from a monomer (b-1) having a carboxy group and a structural unit derived from a monomer (b-2) having a polyoxyalkylene group
• the solvent C contains at least one selected from the group consisting of water, aliphatic monoalcohols having 1 to 4 carbon atoms and ketones having 3 to 4 carbon atoms
• the content of the metal fine particles a is 8% by mass or more and 17% by mass or less
• the mass ratio of the content of the polymer B to the total amount of the content of the polymer B and the content of the metal fine particles a [polymer B/(polymer B + metal fine particles a)] is 0.05 or more and 0.17 or less.
• an ink containing fine metal particles Containing metal fine particles a dispersed with polymer B, formic acid and solvent C,
• the metal fine particles a contain silver
• the polymer B comprises a vinyl-based polymer containing a structural unit derived from a monomer (b-1) having a carboxy group and a structural unit derived from a monomer (b-2) having a polyoxyalkylene group
• the solvent C contains at least one selected from the group consisting of water, aliphatic monoalcohols having 1 to 4 carbon atoms and ketones having 3 to 4 carbon atoms,
• the content of the metal fine particles a is 8% by mass or more and 17% by mass or less
• the mass ratio of the content of the polymer B to the total amount of the content of the polymer B and the content of the metal fine particles a [polymer B/(polymer B + metal fine particles a)] is 0.05 or more and 0.17 or less.
• an ink containing fine metal particles Containing metal fine particles a dispersed with polymer B, formic acid and solvent C,
• the metal fine particles a contain silver
• the polymer B contains structural units derived from the monomer (b-1) having a carboxy group, structural units derived from the monomer (b-2) having a polyoxyalkylene group, and structural units derived from the hydrophobic monomer (b-3). including a vinyl polymer
• the solvent C contains at least one selected from the group consisting of water, aliphatic monoalcohols having 1 to 4 carbon atoms and ketones having 3 to 4 carbon atoms, The solvent C has a boiling point of 70° C. or higher and 105° C.
• the content of the metal fine particles a is 8% by mass or more and 17% by mass or less
• the mass ratio of the content of the polymer B to the total amount of the content of the polymer B and the content of the metal fine particles a [polymer B/(polymer B + metal fine particles a)] is 0.05 or more and 0.155 or less.
• the polymer B is a structural unit derived from at least one selected from (meth)acrylic acid and maleic acid as the monomer (b-1), and a structural unit derived from alkoxypolyalkylene glycol (meth)acrylate as the monomer (b-2).
• the ink containing fine metal particles according to any one of ⁇ 20> to ⁇ 22>, which contains a vinyl polymer containing ⁇ 24>
• the polymer B has a structural unit derived from at least one selected from (meth)acrylic acid and maleic acid as the monomer (b-1), a structural unit derived from an alkoxypolyalkylene glycol (meth)acrylate as the monomer (b-2), And any of ⁇ 20> to ⁇ 23>, comprising a structural unit derived from at least one selected from (meth)acrylates having a hydrocarbon group derived from a styrene monomer and an aliphatic alcohol as the monomer (b-3) Ink containing fine metal particles as described above.
• ⁇ 25> The metal according to any one of ⁇ 20> to ⁇ 24>, wherein the solvent C contains at least one selected from methanol, ethanol, n-propanol, isopropanol, isobutanol, n-butanol, acetone, methyl ethyl ketone, and water.
• Inks containing fine particles ⁇ 26> The ink containing fine metal particles according to any one of ⁇ 20> to ⁇ 25>, wherein the solvent C contains at least one selected from ethanol, n-propanol, isopropanol, methyl ethyl ketone and water.
• the content of fine metal particles a is 8% by mass or more and 17% by mass or less
• the content of polymer B is 0.7% by mass or more and 2.5% by mass or less
• the content of formic acid is 0.8%.
• the ink containing fine metal particles according to any one of ⁇ 20> to ⁇ 26>, wherein the content of solvent C is 70% by mass or more and 90% by mass or less.
• ⁇ 29> The ink containing fine metal particles according to any one of ⁇ 21> to ⁇ 28>, wherein the content of silver in the fine metal particles a is 80% by mass or more.
• the content of the vinyl polymer containing the structural unit derived from the monomer (b-1) having a carboxy group and the structural unit derived from the monomer (b-2) having a polyoxyalkylene group in the polymer B is 80% by mass or more.
• the structural unit derived from the monomer (b-1) having a carboxy group the structural unit derived from the monomer (b-2) having a polyoxyalkylene group and the structural unit derived from the hydrophobic monomer (b-3)
• ⁇ 32> In the polymer B, a structural unit derived from at least one selected from (meth)acrylic acid and maleic acid as the monomer (b-1) and a structural unit derived from an alkoxypolyalkylene glycol (meth)acrylate as the monomer (b-2)
• the ink containing fine metal particles according to any one of ⁇ 23> to ⁇ 31>, wherein the content of the vinyl polymer containing is 80% by mass or more.
• the content of a vinyl polymer containing a structural unit derived from at least one selected from styrene monomers and (meth)acrylates having a hydrocarbon group derived from an aliphatic alcohol as the monomer (b-3) is 80% by mass or more.
• the ink containing fine metal particles according to any one of ⁇ 24> to ⁇ 32>, wherein: ⁇ 34> Any one of ⁇ 20> to ⁇ 33>, wherein the total content of water in solvent C, an aliphatic monoalcohol having 1 to 4 carbon atoms, and a ketone having 3 to 4 carbon atoms is 80% by mass or more. Ink containing fine metal particles.
• ⁇ 35> Any of ⁇ 25> to ⁇ 34>, wherein the total content of methanol, ethanol, n-propanol, isopropanol, isobutanol, n-butanol, acetone, methyl ethyl ketone, and water in solvent C is 80% by mass or more Ink containing fine metal particles as described above.
• ⁇ 37> An inkjet printing ink containing the metal fine particle-containing ink according to any one of ⁇ 20> to ⁇ 36> and a surfactant.
• At least one ink selected from the group consisting of the metal fine particle-containing ink according to any one of ⁇ 20> to ⁇ 36> and the inkjet printing ink according to ⁇ 37> is applied onto a substrate, and a metal film is formed.
• a method for producing printed matter comprising step 5 of obtaining a formed printed matter.
• the method for producing a printed matter according to ⁇ 38>, wherein the method for applying the ink onto the substrate is an inkjet printing method.
• GPC device "HLC-8320GPC” manufactured by Tosoh Corporation Column: “TSKgel SuperAWM-H, TSKgel SuperAW3000, TSKgel guardcolumn Super AW-H” manufactured by Tosoh Corporation Eluent: a solution in which phosphoric acid and lithium bromide were dissolved in N,N-dimethylformamide at concentrations of 60 mmol/L and 50 mmol/L, respectively Flow rate: 0.5 mL/min Standard material: monodisperse polystyrene kit manufactured by Tosoh Corporation “PStQuick B (F-550, F-80, F-10, F-1, A-1000), PStQuick C (F-288, F-40, F-4 , A-5000, A-500)”
• PStQuick B F-550, F-80, F-10, F-1, A-1000
• PStQuick C F-288, F-40, F-4 , A-5000, A-500
• the cumulant average particle size of the fine metal particles a in the ink containing fine metal particles was measured by cumulant analysis using a laser particle analysis system "ELS-8000" (manufactured by Otsuka Electronics Co., Ltd.).
• the measurement conditions were a temperature of 25° C., an angle between the incident light and the detector of 90°, and the number of times of accumulation of 100 times. It is 5 ⁇ 10 ⁇ 3 mass % (converted to solid concentration).
• Polymer B-2 Produced by the following method.
• thermometer two dropping funnels with a 100 mL nitrogen bypass, a 1000 mL four-necked round-bottom flask equipped with a reflux device, ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) 20.0 g was put and put in an oil bath. After heating the inner temperature of the flask to 80° C., nitrogen bubbling was performed for 10 minutes.
• methacrylic acid manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., special grade reagent
• styrene manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., special grade reagent
• methyl methacrylate manufactured by, special grade reagent
• 7.2 g methoxypolyethylene glycol (EO23 mol) methacrylate (manufactured by NOF Corporation "PME-1000") 67.5 g
• 3-mercaptopropionic acid Flujifilm Wako Pure Chemical Co., Ltd., special grade reagent
• 28.7 g of ethanol were dissolved in a poly beaker and placed in the dropping funnel (1).
• the resin solution is dried using a freeze dryer (manufactured by Tokyo Rikakikai Co., Ltd., model: FDU-2110) equipped with a dry chamber (manufactured by Tokyo Rikakikai Co., Ltd., model: DRC-1000). Freeze for 1 hour, reduce pressure at -10°C for 9 hours, reduce pressure at 25°C for 5 hours, and freeze-dry at a reduced pressure of 5 Pa) to obtain absolute dry polymer B-2 (methacrylic acid/methyl methacrylate/styrene/methoxypolyethylene glycol ( EO (23 mol)) methacrylate polymer, acid value: 100 mgKOH/g, Mn: 8,300) was obtained.
• Example 1 Production of ink containing fine metal particles (step 1) In a 1,000 mL stainless steel separable flask equipped with a thermometer, a 100 mL nitrogen bypass dropping funnel, and a reflux device, ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent, concentration 95%, 5 % water), 60 g of polymer B-1, and 300 g of silver oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) as metal oxide A are added, Dispa type stirring blades (Shinto Kagaku The mixture was stirred at 25° C.
• Step 2 The mixture 1 was stirred in a water bath at a stirring rate of 3,000 rpm for 2 hours while controlling the temperature at 60° C. After air cooling, a dark brown metal fine particle dispersion of Synthesis Example 1 was obtained.
• Step 3 30.00 g of the metal fine particle dispersion of Synthesis Example 1 obtained in Step 2, ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent, concentration 95%, containing 5% water) and 68.86 g of formic acid (Fuji Film Wako Pure Chemical Co., Ltd., special grade reagent, concentration 88%, containing 12% water) was mixed for 30 minutes at 25 ° C. using a magnetic stirrer (diameter 20 mm) at a stirring speed of 200 rpm. , an ink 1 containing fine metal particles was obtained.
• the obtained metal fine particle-containing inks 1 to 20 were each subjected to evaluation by the following methods.
• Table 4 shows the results.
• step 4 Production of inkjet printing ink (step 4) In a 300 mL polyethylene beaker, 100 g of the metal fine particle-containing ink obtained in Examples and Comparative Examples, and an acetylene glycol surfactant ("Surfinol 104PG-50" manufactured by Nissin Chemical Industry Co., Ltd., 2, 4, 0.2 g of a propylene glycol solution of 7,9-tetramethyl-5-decyne-4,7-diol (effective content 50%) was added, and the mixture was stirred with a magnetic stirrer at 25° C. for 30 minutes.
• an acetylene glycol surfactant "Surfinol 104PG-50" manufactured by Nissin Chemical Industry Co., Ltd., 2, 4, 0.2 g of a propylene glycol solution of 7,9-tetramethyl-5-decyne-4,7-diol (effective content 50%) was added, and the mixture was stirred with a magnetic stirrer at 25°
• the resulting ink for inkjet printing was filtered using a 5 ⁇ m disposable membrane filter (Minisart, manufactured by Sartorius, hole diameter: 5 ⁇ m) to obtain an ink for inkjet printing.
• the obtained ink for inkjet printing was evaluated by the following methods.
• Ejectability was evaluated using a liquid observation device (manufactured by Meteor Inkjet) attached to the inkjet printing evaluation device.
• the ejection state was observed 0, 5, 10, 15, 20, 25 and 30 minutes after the start of ejection, and the point at which ejection deviation or nozzle clogging occurred was defined as the continuous ejection possible time.
• Table 4 shows the results. Ejectability is better as the continuous ejection time is longer.
• a state in which no ejection occurred or a nozzle missing at the time of initial ejection was evaluated as x in the initial ejection.
• the metal fine particle-containing inks of Examples 1-16 had better volume resistivity and ejection properties in inkjet printing than the metal fine particle-containing inks of Comparative Examples 1-4. Furthermore, the metal fine particle-containing inks of Examples 1 to 16 used solvents with low boiling points, so that they dried quickly and did not require replacement of the solvent.

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