WO2022145077A1 - 金属微粒子含有インク - Google Patents
金属微粒子含有インク Download PDFInfo
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- WO2022145077A1 WO2022145077A1 PCT/JP2021/024501 JP2021024501W WO2022145077A1 WO 2022145077 A1 WO2022145077 A1 WO 2022145077A1 JP 2021024501 W JP2021024501 W JP 2021024501W WO 2022145077 A1 WO2022145077 A1 WO 2022145077A1
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- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 1
- 150000003941 n-butylamines Chemical class 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 125000004888 n-propyl amino group Chemical class [H]N(*)C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical compound CC(O)CC(C)O GTCCGKPBSJZVRZ-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- OJTDGPLHRSZIAV-UHFFFAOYSA-N propane-1,2-diol Chemical compound CC(O)CO.CC(O)CO OJTDGPLHRSZIAV-UHFFFAOYSA-N 0.000 description 1
- SXBRULKJHUOQCD-UHFFFAOYSA-N propanoic acid Chemical compound CCC(O)=O.CCC(O)=O SXBRULKJHUOQCD-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- 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
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
- C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0425—Copper-based alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0433—Nickel- or cobalt-based alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0466—Alloys based on noble metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/10—Formation of a green body
- B22F10/16—Formation of a green body by embedding the binder within the powder bed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0242—Shape of an individual particle
- H05K2201/0257—Nanoparticles
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
- H05K3/125—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing by ink-jet printing
Definitions
- the present invention relates to an ink containing metal fine particles and a method for producing a printed matter using the ink.
- Patent Document 1 uses metal nanoparticles for the purpose of providing metal colloidal particles having few coarse particles and excellent long-term storage stability containing metal nanoparticles at a high concentration.
- the present invention is a metal fine particle-containing ink containing metal fine particles A, carboxylic acid C, and amine D dispersed in polymer B.
- Polymer B has at least one selected from organic acid groups and organic base groups.
- Carboxylic acid C has 1 or more and 6 or less carbon atoms.
- Amine D has 1 or more and 6 or less carbon atoms.
- the content of carboxylic acid C is 0.7% by mass or more and 15% by mass or less.
- the present invention relates to a metal fine particle-containing ink having an amine D content of 0.7% by mass or more and 20% by mass or less.
- Inks containing metal fine particles are required to be printed on a flexible base material such as paper or a resin film and used for conductive applications in printed electronics and decorative applications for imparting mirror gloss.
- a flexible base material such as paper or a resin film
- the metal film tends to be cracked when the flexible base material is bent.
- cracks in the metal film reduce conductivity and mirror gloss, it is required to improve the bending resistance of the obtained printed matter.
- the ink containing the metal fine particles is forced to be stored in a refrigerator due to the dispersion stability of the metal fine particles, the workability when using the ink may be impaired, and the workability is impaired in an environment of room temperature (25 ° C.) or higher. Also, it is required to have excellent storage stability.
- Patent Document 1 does not have sufficient storage stability and bending resistance.
- the present invention relates to a metal fine particle-containing ink capable of obtaining a printed matter having excellent storage stability and excellent bending resistance, and a method for producing a printed matter using the ink.
- the present inventors have a metal fine particle-containing ink containing metal fine particles, a carboxylic acid, and an amine dispersed in a polymer, wherein the polymer has at least one selected from an organic acid group and an organic base group.
- the carbon number of the carboxylic acid and the amine and the content in the ink are each within a predetermined range, the dispersion stability of the metal fine particles can be improved, a good metal film can be formed, and storage stability can be achieved. It has been found that it is possible to provide a metal fine particle-containing ink capable of obtaining a printed matter having excellent properties and excellent bending resistance, and a method for producing a printed matter using the ink. That is, the present invention relates to the following [1] and [2].
- Polymer B has at least one selected from organic acid groups and organic base groups.
- Carboxylic acid C has 1 or more and 6 or less carbon atoms.
- Amine D has 1 or more and 6 or less carbon atoms.
- the content of carboxylic acid C is 0.7% by mass or more and 15% by mass or less.
- a metal fine particle-containing ink capable of obtaining a printed matter having excellent storage stability and excellent bending resistance, and a method for producing a printed matter using the ink.
- the metal fine particle-containing ink of the present invention is a metal fine particle-containing ink containing metal fine particles A, carboxylic acid C, and amine D dispersed in the polymer B, and the polymer B is composed of an organic acid group and an organic base group. It has at least one selected, the carbon number of the carboxylic acid C is 1 or more and 6 or less, the carbon number of the amine D is 1 or more and 6 or less, and the content of the carboxylic acid C is 0.7 mass by mass. % Or more and 15% by mass or less, and the content of amine D is 0.7% by mass or more and 20% by mass or less.
- the metal fine particles contained in the ink of the present invention are dispersed in a polymer having at least one selected from an organic acid group and an organic base group, and it is considered that the dispersion stability of the metal fine particles is improved. Furthermore, since each of the low molecular weight carboxylic acid and the low molecular weight amine having a predetermined carbon number is contained in a predetermined ratio, the metal fine particles are affected by the interaction between the polymer, the low molecular weight carboxylic acid, and the low molecular weight amine. It is considered that the dispersion stability is improved.
- the storage stability is improved due to the synergistic effect on the dispersion stability of these metal fine particles.
- the polymer in which the metal fine particles are dispersed is replaced with the low molecular weight carboxylic acid and the low molecular weight amine in the drying process of the ink, and the low molecular weight carboxylic acid and the low molecular weight amine are further removed.
- the ink solvent gradually volatilizes from the ink film, giving a grace period for rearranging the metal fine particles.
- the printed matter having a dense metal film can be obtained and the bending resistance of the printed matter is improved.
- the volume resistivity can be reduced by forming this dense metal film.
- inkjet printing is used as the printing method, as an index of printing reliability, the open time characteristics that can satisfactorily eject ink even when printing is resumed after printing is paused for a predetermined time are improved. It has been demanded.
- the complex formed from the low molecular weight carboxylic acid and the low molecular weight amine exhibits a pseudo-high boiling point compound-like function as well as the improvement of the dispersion stability of the metal fine particles, and the ink jet is used. It is considered that the drying of the ink in the vicinity of the nozzle of the head is suppressed and the open time characteristics are also improved.
- this composition it is possible to highly achieve both the storage stability of the ink containing metal fine particles, the open time characteristics in inkjet printing, and the bending resistance of the printed matter.
- the metals (metal atoms) constituting the metal fine particles A are group 4 transition metals such as titanium and zirconium, group 5 transition metals such as vanadium and niob, and group 6 transition metals such as chromium, molybdenum, and tungsten. , Group 7 transition metals such as manganese, technetium and renium, Group 8 transition metals such as iron and ruthenium, Group 9 transition metals such as cobalt, rhodium and iridium, and group 10 transition metals such as nickel, palladium and platinum.
- group 4 transition metals such as titanium and zirconium
- group 5 transition metals such as vanadium and niob
- group 6 transition metals such as chromium, molybdenum, and tungsten.
- Group 7 transition metals such as manganese, technetium and renium
- Group 8 transition metals such as iron and ruthenium
- Group 9 transition metals such as cobalt, r
- 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, etc. 14th group metal and the like.
- the metal constituting the metal fine particles A one kind may be used as a single metal, or two or more kinds may be used in combination as an alloy. Among them, the metal fine particles A from the viewpoints of conductivity, decorativeness, dispersion stability of metal fine particles to improve storage stability and open time characteristics of ink, and bending resistance.
- the metals constituting the above are preferably groups 4 to 11 and contain transition metals of the 4th to 6th cycles, more preferably containing noble metals such as copper, nickel, gold, silver, platinum and palladium, and further. It preferably contains at least one selected from gold, silver, copper, nickel, and palladium, more preferably contains at least one selected from gold, silver, copper, and nickel, and even more preferably silver, copper, and nickel. It contains at least one selected from, more preferably contains silver, and even more preferably silver.
- the type of metal can be confirmed by high frequency inductively coupled plasma emission spectrometry.
- the total content of silver, copper, and nickel in the metal fine particles A improves the storage stability and open-time characteristics of the ink by improving the viewpoint of conductivity, decorativeness, and dispersion stability of the metal fine particles. From the viewpoint of improving bending resistance, 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 substantially. It is 100% by mass.
- the silver content in the metal fine particles A improves the conductivity, the decorativeness, the dispersion stability of the metal fine particles, and the storage stability and the open time characteristics of the ink, and the bending resistance.
- substantially 100% by mass means that components contained unintentionally may be contained. Examples of unintentionally contained components include unavoidable impurities.
- the metal fine particles A according to the present invention have a viewpoint of improving the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, a viewpoint of improving bending resistance, and a viewpoint of reducing the volume resistivity. Therefore, it is dispersed with the polymer B.
- Polymer B has at least one selected from organic acid groups and organic base groups. Examples of the organic acid group include a carboxy group (-COOM), a sulfonic acid group (-SO 3 M), a phosphoric acid group (-OPO 3 M 2 ), and the like, which are acidified by dissociating and releasing hydrogen ions.
- the organic acid group has a viewpoint of improving the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, a viewpoint of improving bending resistance, and a viewpoint of reducing the volume resistivity. Therefore, it is preferably a carboxy group.
- Groups (-N + R 1 R 2 R 3 ) and the like can be mentioned.
- R 1 to R 3 represent a methyl group, an ethyl group, a propyl group, an isopropyl group, a hydroxymethyl group, or a hydroxyethyl group.
- the organic base group has a viewpoint of improving the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the viewpoint of reducing the volume resistance.
- the polymer B is preferably carboxy from the viewpoint of improving the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the viewpoint of reducing the volume resistivity. It contains at least one selected from a group and an imino group, more preferably a carboxy group.
- the polymer B is preferably organic from the viewpoint of improving the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the viewpoint of reducing the volume resistance. It is at least one selected from a polymer BI having an acid group and a polymer BII having an organic base group, and more preferably a polymer BI having an organic acid group.
- Polymer B is preferably water-soluble from the viewpoint of improving the dispersion stability of the metal fine particles to improve the storage stability and open-time characteristics of the ink, improving the bending resistance, and reducing the volumetric resistance.
- 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 10 g or more. It means that it is preferably more than 10 g.
- the dissolved amount of the polymer B is, for example, the dissolved amount when the organic acid group of the polymer BI is 100% neutralized with sodium hydroxide in the case of the polymer BI, and the dissolved amount in the case of the polymer BII. It is the amount of dissolution when the organic base group of is 100% neutralized with hydrochloric acid.
- the polymer B is preferably poly from the viewpoint of improving the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the viewpoint of reducing the volume resistivity. It has an alkylene glycol chain.
- the polyalkylene glycol chain preferably contains units derived from alkylene oxide having 2 or more and 4 or less carbon atoms such as ethylene oxide, propylene oxide and butylene oxide, and more preferably contains units derived from ethylene oxide or units derived from propylene oxide. More preferably, it contains a unit derived from ethylene oxide.
- Polymer BI has an organic acid group.
- organic acid groups are similar to those exemplified above.
- the organic acid group of the polymer BI is preferably a carboxy group.
- the basic structure of the polymer BI include vinyl-based polymers such as acrylic resin, styrene-based resin, styrene-acrylic resin, and acrylic silicone-based resin; and condensation-based polymers such as polyester and polyurethane.
- polymer BI is carboxy from the viewpoint of improving the dispersion stability of metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the viewpoint of reducing the volume resistivity.
- a vinyl-based polymer containing a structural unit derived from the monomer (b-1) having a group is preferable.
- the vinyl-based polymer is preferably a homopolymer composed of a structural unit derived from the monomer (b-1), or is derived from the structural unit derived from the monomer (b-1) and a monomer other than the monomer (b-1). It is a copolymer containing a structural unit.
- the vinyl-based polymer may be a block copolymer, a random copolymer, or an alternate copolymer.
- Examples of the monomer (b-1) include 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. And so on.
- 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 used from the viewpoint of improving the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the viewpoint of reducing the volume resistivity.
- (meth) acrylic acid means at least one selected from acrylic acid and methacrylic acid.
- (Meta) acrylic acid in the following is also synonymous.
- the polymer BI is preferably carboxy from the viewpoint of improving the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the viewpoint of reducing the volume resistivity. It is a vinyl-based polymer containing a structural unit derived from a monomer (b-1) having a group and a structural unit derived from a hydrophobic monomer (b-2).
- hydrophobic monomer means that when the monomer is dissolved in 100 g of ion-exchanged water at 25 ° C. until it is saturated, the amount of the monomer dissolved is less than 10 g.
- the dissolved amount of the monomer (b-2) is preferably 5 g or less, more preferably 1 g or less, from the same viewpoint as described above.
- Examples of the monomer (b-2) include styrene-based monomers and (meth) acrylic acid esters.
- styrene is used from the viewpoint of improving the dispersion stability of metal fine particles to improve the storage stability and open time characteristics of the ink, improving the bending resistance, and reducing the volume resistance.
- ⁇ -Methylstyrene, 2-methylstyrene, 4-vinyltoluene (4-methylstyrene), divinylbenzene (vinylstyrene) and other styrene and styrene derivatives are preferable, and styrene and ⁇ -methylstyrene are more preferable.
- Examples of the (meth) acrylic acid ester include an aromatic group-containing (meth) acrylic acid ester and a (meth) acrylic acid ester having a hydrocarbon group derived from an aliphatic alcohol.
- the aromatic group-containing (meth) acrylic acid ester has a viewpoint of improving the dispersion stability of metal fine particles to improve the storage stability and open time characteristics of the ink, a viewpoint of improving bending resistance, and a volume resistance.
- Phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like are preferable, and benzyl (meth) acrylate is more preferable, from the viewpoint of reducing the amount of phenyl (meth) acrylate.
- the dispersion stability of metal fine particles is improved, and the storage stability and open-time characteristics of the ink are improved, and the bending resistance is improved.
- it preferably has a hydrocarbon group derived from an aliphatic alcohol having 1 or more and 22 or less carbon atoms.
- Examples thereof include (meth) acrylate having a group.
- the (meth) acrylic acid ester having a hydrocarbon group derived from an aliphatic alcohol is more preferably one having an alkyl group having 6 or more and 10 or less carbon atoms.
- the monomer (b-2) may be used alone or in combination of two or more.
- “(meth) acrylate” is at least one selected from acrylates and methacrylates.
- the "(meth) acrylate” in the following is also synonymous.
- the monomer (b-2) improves the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, from the viewpoint of improving the bending resistance, and from the viewpoint of reducing the volume resistance.
- at least one selected from styrene-based monomers and (meth) acrylic acid esters Preferably at least one selected from styrene-based monomers and (meth) acrylic acid esters, more preferably at least one selected from styrene, styrene derivatives, and (meth) acrylic acid esters, and even more preferably styrene.
- styrene derivatives more preferably at least one selected from styrene, ⁇ -methylstyrene, 2-methylstyrene and 4-vinyltoluene (4-methylstyrene), even more preferably.
- the polymer B has a polyalkylene glycol chain
- the polymer BI improves the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the volume.
- it is preferably a vinyl-based polymer further containing a structural unit derived from a monomer (b-3) having a polyoxyalkylene group.
- the monomer (b-3) include polyalkylene glycol (meth) acrylate, alkoxypolyalkylene glycol (meth) acrylate, and phenoxypolyalkylene glycol (meth) acrylate.
- the monomer (b-3) may be used alone or in combination of two or more.
- the monomer (b-3) has a viewpoint of improving the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the viewpoint of reducing the volume resistance.
- the alkoxy group of the alkoxypolyalkylene glycol (meth) acrylate preferably has 1 or more and 8 or less carbon atoms, and more preferably 1 or more and 4 or less carbon atoms.
- alkoxypolyalkylene glycol (meth) acrylate examples include methoxypolyalkylene glycol (meth) acrylate, ethoxypolyalkylene glycol (meth) acrylate, propoxypolyalkylene glycol (meth) acrylate, butoxypolyalkylene glycol (meth) acrylate, and octoxy.
- alkoxypolyalkylene glycol (meth) acrylate examples include methoxypolyalkylene glycol (meth) acrylate, ethoxypolyalkylene glycol (meth) acrylate, propoxypolyalkylene glycol (meth) acrylate, butoxypolyalkylene glycol (meth) acrylate, and octoxy.
- examples thereof include polyalkylene glycol (meth) acrylate.
- the polyoxyalkylene group of the monomer (b-3) preferably contains a unit derived from an alkylene oxide having 2 or more and 4 or less carbon atoms.
- alkylene oxide include ethylene oxide, propylene oxide and butylene oxide.
- the polyoxyalkylene group has a viewpoint of improving the dispersion stability of metal fine particles to improve the storage stability and open time characteristics of the ink, a viewpoint of improving bending resistance, and a viewpoint of reducing volume resistivity. Therefore, it more preferably contains a unit derived from ethylene oxide.
- the number of units derived from the alkylene oxide in the polyoxyalkylene group improves the dispersion stability of the metal fine particles, improves the storage stability and open time characteristics of the ink, improves the bending resistance, and the volume. From the viewpoint of reducing the resistivity, it is preferably 2 or more, more preferably 5 or more, still more preferably 7 or more, and preferably 100 or less, more preferably 70 or less, still more preferably 50 or less, still more preferably. It is 40 or less, more preferably 30 or less, and even more preferably 20 or less.
- the polyoxyalkylene group improves the dispersion stability of the metal fine particles, improves the storage stability and open time characteristics of the ink, improves the bending resistance, and reduces the volume resistivity.
- It may be a copolymer containing a unit derived from ethylene oxide and a unit derived from propylene oxide.
- the molar ratio [EO / PO] of the unit (EO) derived from ethylene oxide and the unit (PO) derived from propylene oxide is preferably 60/40 or more, more preferably 65/35 or more, still more preferably 70/30 or more. Yes, and preferably 90/10 or less, more preferably 85/15 or less, still more preferably 80/20 or less.
- the copolymer containing a unit derived from ethylene oxide and a unit derived from propylene oxide may be a block copolymer, a random copolymer, or an alternate copolymer.
- Examples thereof include 800, 1000 and the like, Blemmer AP-150, 400, 550 and the like, Blemmer 50PEP-300, Blemmer 50POEP-800B, Blemmer 43PAPE-600B and the like.
- the polymer BI is a vinyl-based polymer containing a structural unit derived from the monomer (b-1) and a structural unit derived from the monomer (b-2)
- the content of each monomer in the raw material monomer at the time of producing the polymer BI (Content as unneutralized amount; the same applies hereinafter) or the content of the structural unit derived from each monomer in the polymer BI improves the dispersion stability of the metal fine particles and improves the storage stability and open time characteristics of the ink. From the viewpoint of improving, improving the bending resistance, and reducing the volume resistance, it is as follows.
- the content of the monomer (b-1) is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and preferably 20% by mass or less, more preferably 20% by mass or less. It is 10% by mass or less, more preferably 5% by mass or less.
- the content of the monomer (b-2) is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and preferably 98% by mass or less, more preferably 90% by mass. % Or less, more preferably 80% by mass or less, still more preferably 70% by mass or less.
- the mass ratio of the monomer (b-1) to the monomer (b-2) [monomer (b-1) / monomer (b-2)] is preferably 0.01 or more, more preferably 0.02 or more, still more preferable. Is 0.03 or more, more preferably 0.04 or more, and preferably 1 or less, more preferably 0.5 or less, still more preferably 0.1 or less, still more preferably 0.07 or less, and more. More preferably, it is 0.05 or less.
- the polymer BI is a vinyl-based polymer containing a structural unit derived from the monomer (b-1) and a structural unit derived from the monomer (b-2), and further containing a structural unit derived from the monomer (b-3), the polymer.
- the content of the monomer (b-3) in the raw material monomer or the content of the structural unit derived from the monomer (b-3) in the polymer BI at the time of BI production improves the dispersion stability of the metal fine particles, and the ink From the viewpoint of improving the storage stability and open time characteristics, improving the bending resistance, and reducing the volume resistance, it is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15. By mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less. ..
- the polymer BI one synthesized by a known method may be used, or a commercially available product may be used. Examples of commercially available polymer BI products include DISPERBYK-190 and 2015 manufactured by BYK.
- the polymer BI improves the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, and from the viewpoint of improving the bending resistance, the viewpoint of improving the low temperature sintering property and the low temperature bonding property.
- a structural unit derived from the monomer (b-1) having a carboxy group preferably a structural unit derived from the hydrophobic monomer (b-2), and a monomer having a polyoxyalkylene group (b).
- the structural unit derived from (b-1) is preferably 0.5% by mass or more and 20% by mass or less, and the structural unit derived from (b-2) is 30% by mass. It is a vinyl-based polymer having a content of% or more and 90% by mass or less and a constituent unit derived from (b-3) of 5% by mass or more and 50% by mass or less, and more preferably, the constituent unit derived from (b-1) is 0.
- the constituent unit derived from (b-2) is 30% by mass or more and 70% by mass or less
- the constituent unit derived from (b-3) is 20% by mass or more and 50% by mass or less. It is a vinyl-based polymer.
- the number average molecular weight Mn of the polymer BI is from the viewpoint of improving the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the viewpoint of reducing the volume resistivity. Therefore, it is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more, still more preferably 5,000 or more, and preferably 100,000 or less, more preferably 50, It is 000 or less, more preferably 30,000 or less, and 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 the polymer BI is determined from the viewpoint of improving the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, improving the bending resistance, and reducing the volume resistance. It is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and preferably 800 mgKOH / g or less, more preferably 600 mgKOH / g or less, still more preferably 400 mgKOH / g or less.
- the acid value of the polymer BI can also be calculated from the mass ratio of the constituent monomers. It can also be obtained by a method of dissolving or swelling the polymer in an appropriate solvent and titrating it.
- Polymer BII has an organic base group.
- organic base groups are similar to those exemplified above.
- the organic base group of the polymer BII is preferably a secondary amino group, more preferably an imino group.
- the polymer BII include polyalkyleneimine, polyallylamine, polyvinylamine and the like.
- polymer BII is a poly from the viewpoint of improving the dispersion stability of metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the viewpoint of reducing the volume resistivity. Alkyleneimine is preferred.
- alkyleneimine constituting the polyalkyleneimine
- examples of the alkyleneimine constituting the polyalkyleneimine include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,1-dimethylethyleneimine and other alkyleneimines having 2 or more and 8 or less carbon atoms.
- ethylene is preferable from the viewpoint of improving the dispersion stability of metal fine particles to improve the storage stability and open time characteristics of the ink.
- the viewpoint of improving the bending resistance, and the viewpoint of reducing the volume resistance ethylene is preferable.
- the alkyleneimine may be used alone or in combination of two or more.
- the polyalkyleneimine may be linear or branched. When the polyalkyleneimine is branched, it may have a tertiary amino group or a primary amino group in addition to the secondary amino group (imino group) in its structure.
- the weight average molecular weight Mw of the polyalkyleneimine improves the dispersion stability of the metal fine particles, improves the storage stability and open time characteristics of the ink, improves the bending resistance, and reduces the volume resistivity. From the viewpoint, it is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, still more preferably 7,000 or more, and preferably 200,000 or less, more preferably 100. It is 000 or less, more preferably 50,000 or less, still more preferably 30,000 or less, still more preferably 15,000 or less.
- the above weight average molecular weight Mw can be measured by gel permeation chromatography (GPC).
- polyalkyleneimine one synthesized by a known method may be used, or a commercially available product may be used.
- a method for synthesizing polyethyleneimine a method of ring-opening polymerization of ethyleneimine using carbon dioxide, hydrochloric acid, hydrobromic acid, etc. as a catalyst, a method of polycondensing ethylene chloride and ethylenediamine, a method of heating 2-oxazolidone, etc.
- Polyalkyleneimine can be used alone or in combination of two or more.
- the polymer B has a polyalkylene glycol chain
- the polymer BII improves the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the volume.
- a PAI / PAO copolymer having a polyalkyleneimine (hereinafter, also referred to as “PAI”) chain and a polyalkylene glycol (polyalkylene oxide) (hereinafter, also referred to as “PAO”) chain is preferable. It is preferably coalesced.
- the PAO chain constituting the PAI / PAO copolymer improves the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the volume resistivity.
- a unit derived from an alkylene oxide having 2 or more and 4 or less carbon atoms such as ethylene oxide, propylene oxide and butylene oxide, and a polyethylene oxide chain containing a unit derived from ethylene oxide is more preferable.
- the PAI / PAO copolymer is preferably a PAI / PAO graft copolymer having a PAI chain as a trunk and a PAO chain as a branch, and a PAI / PAO in which a PAO chain is bonded to a mesh-like PAI chain via an amino group. It is at least one selected from a copolymer and a PAI / PAO block copolymer having a PAI chain and a PAO chain.
- Examples of the form of the PAI / PAO graft copolymer include a form in which the PAI chain as a stem is linear and a form in which the PAI chain as a stem is branched.
- Examples of the binding form of the polymer block of the PAI / PAO block copolymer include diblock and triblock, and specific examples of the PAI / PAO block copolymer include PAI / PAO diblock copolymer and PAI /. Examples thereof include PAO / PAI triblock copolymers.
- the weight average molecular weight Mw of the PAI chain constituting the PAI / PAO copolymer is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 7,000 or more, still more preferably 10,000 or more. Yes, and preferably 100,000 or less, more preferably 70,000 or less, still more preferably 50,000 or less.
- the weight average molecular weight Mw of the PAO chain constituting the PAI / PAO copolymer is preferably 300 or more, more preferably 500 or more, still more preferably 1,000 or more, and preferably 50,000 or less, more preferably. Is 30,000 or less, more preferably 20,000 or less.
- the above weight average molecular weight Mw is determined by measuring the weight average molecular weight Mw of the raw materials PAI chain compound and PAO chain compound used in the production of the PAI / PAO copolymer using gel permeation chromatography (GPC). Can be done.
- the average number of grafted PAO chains per PAI chain is preferably 5 or more, more preferably 10 or more, still more preferably 13 or more, and preferably 50 or less. , More preferably 40 or less, still more preferably 35 or less.
- the ratio of the total number of alkyleneimine units having grafted PAO chains to the total number of alkyleneimine units is It is preferably 0.01 or more, more preferably 0.015 or more, still more preferably 0.02 or more, and preferably 0.1 or less, more preferably 0.07 or less, still more preferably 0.05 or less. Is.
- the above ratio can be measured by 1 H-NMR.
- the PAI / PAO copolymer is a method of reacting a polyalkyleneimine with a polyoxyalkylene having a functional group capable of reacting with the nitrogen atom of the polyalkyleneimine, a method of adding an alkylene oxide to the nitrogen atom of the polyalkyleneimine, and the like. Can be obtained by Examples of the polyoxyalkylene having a functional group capable of reacting with the nitrogen atom of the polyalkyleneimine include methoxypolyethylene glycol acetic acid and the like. Examples of commercially available PAI / PAO copolymers include the PPE series manufactured by Creative PEGWorks.
- the low-temperature sintering property and the low-temperature bonding property are improved from the viewpoint of improving the dispersion stability of the metal fine particles, improving the storage stability and open time characteristics of the ink, and improving the bending resistance.
- the polymer preferably contains at least one selected from a carboxy group and an imino group, and more preferably a structural unit derived from the monomer (b-1) and the monomer (b-2). It is at least one selected from vinyl polymers and polyalkylene imines containing a constituent unit of origin, and more preferably a configuration derived from at least one selected from (meth) acrylic acid and maleic acid as the monomer (b-1).
- the structural unit is 0.5% by mass or more and 20% by mass or less
- the structural unit derived from at least one selected from styrene and styrene derivatives as the monomer (b-2) is 30% by mass or more and 90% by mass or less
- the constituent unit derived from at least one selected from maleic acid is 0.5% by mass or more and 20% by mass or less, and the constituent unit derived from at least one selected from styrene and the styrene derivative as the monomer (b-2) is 30% by mass or more.
- the ink of the present invention is carboxylic from the viewpoint of improving the dispersion stability of metal fine particles, improving the storage stability and open time characteristics of the ink, improving the bending resistance, and reducing the volume resistivity.
- the carbon number of the carboxylic acid C is 1 or more and 6 or less, preferably 1 or more and 3 or less.
- Carboxylic acid C can be used alone or in combination of two or more. Examples of the carboxylic acid C include saturated or unsaturated, linear or branched aliphatic carboxylic acids. Carboxylic acid C may have a functional group other than the carboxy group in the same molecule.
- a functional group having a coordination property with respect to metal fine particles such as a functional group containing at least one heteroatom such as an aldehyde group, a functional group containing a halogen atom, a hydroxy group, and a thiol group.
- metal fine particles such as a functional group containing at least one heteroatom such as an aldehyde group, a functional group containing a halogen atom, a hydroxy group, and a thiol group.
- the same carboxylic acid C is used from the viewpoint of improving the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the viewpoint of reducing the volume resistivity. It is preferable to have an aldehyde group in the molecule.
- carboxylic acid C examples include formic acid, glyoxylic acid, acetic acid, trifluoroacetic acid, propanoic acid (propionic acid), butanoic acid (butyric acid), isobutanoic acid (isobutyric acid), pentanoic acid (valeric acid), and isopentanoic acid.
- Monocarboxylic acids such as (isovaleric acid), pivalic acid, hexane acid (caproic acid), lactic acid; dicarboxylic acids such as oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid; tricarboxylic acids such as citric acid Can be mentioned.
- the boiling point of the carboxylic acid C at 1 atm improves the dispersion stability of the metal fine particles, improves the storage stability and open time characteristics of the ink, improves the bending resistance, and reduces the volume resistivity. From the viewpoint of , More preferably 135 ° C or lower, and even more preferably 115 ° C or lower. When two or more kinds of carboxylic acid C are used, the boiling point of carboxylic acid C is calculated as a weighted average value.
- the carboxylic acid C is preferable from the viewpoint of improving the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, improving the bending resistance, and reducing the volume resistance.
- It contains a monocarboxylic acid, more preferably at least one selected from formic acid, acetic acid, propionic acid, butyric acid, isobutanoic acid, hexane acid, glyoxylic acid and lactic acid, and more preferably formic acid, acetic acid, butyric acid, hexane acid and glyoxyl. It contains at least one selected from acid, more preferably at least one selected from formic acid, hexanoic acid and glyoxylic acid, still more preferably containing at least one selected from formic acid and glyoxylic acid, and even more preferably. Contains formic acid.
- the content of the monocarboxylic acid in the carboxylic acid C improves the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the volume resistance. From the viewpoint of reducing the amount of particles, it is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably substantially 100% by mass. ..
- substantially 100% by mass means that components contained unintentionally may be contained. Examples of the component unintentionally contained include a carboxylic acid C component other than the monocarboxylic acid contained in the carboxylic acid as a raw material.
- the total content of formic acid, acetic acid, propionic acid, butyric acid, isobutanoic acid, hexanoic acid, glyoxylic acid and lactic acid in the carboxylic acid C improves the dispersion stability of the metal fine particles, and the storage stability and open-time characteristics of the ink.
- reducing the volume resistance preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably. It is 98% by mass or more, more preferably substantially 100% by mass.
- substantially 100% by mass means that components contained unintentionally may be contained.
- the components unintentionally contained may be examples thereof include carboxylic acid C components other than formic acid, acetic acid, propionic acid, fatty acid, isobutanoic acid, hexanoic acid, glyoxylic acid and lactic acid contained in the carboxylic acid as a raw material.
- the total content of formic acid and glyoxylic acid in the carboxylic acid C improves the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the volume. From the viewpoint of reducing the resistance, it is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably substantially 100% by mass. Is. Here, "substantially 100% by mass” means that components contained unintentionally may be contained.
- the components unintentionally contained include the formic acid and glyoxyl contained in the carboxylic acid as a raw material.
- the carboxylic acid C component other than the acid include the carboxylic acid C component other than the acid.
- the ink of the present invention is an amine from the viewpoint of improving the dispersion stability of metal fine particles, improving the storage stability and open time characteristics of the ink, improving the bending resistance, and reducing the volume resistivity.
- Contains D The number of carbon atoms of the amine D is 1 or more and 6 or less, preferably 4 or less, more preferably 3 or less from the same viewpoint, and preferably 2 or more from the viewpoint of safety.
- Amine D can be used alone or in combination of two or more.
- Amine D comprises at least one primary amino group, secondary amino group, or tertiary amino group.
- amine D examples include ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, n-butylamine, tert-butylamine, sec-butylamine, and tert-pentylamine.
- Alkylamines such as n-hexylamine, N, N-dimethylethylamine, N, N-diethylmethylamine, N, N-dimethylbutylamine, N-methylpentylamine; monoethanolamine, diethanolamine, triethanolamine, n-propanol Alkanol amines such as amines, isopropanolamines, neopentanolamines, 4-amino-1-butanol, 2-amino-2-methyl-1-propanol; N-methylethanolamine, N-ethylethanolamine, Nn- N-alkyl monoalkanol amines such as butylethanolamine, N-tert-butylethanolamine, 4-ethylamino-1-butanol, 3- (methylamino) -1-propanol, 6-amino-1-hexanol; N- N-alkyldialkanolamines such as methyldiethanolamine, N-e
- the boiling point of amine D at 1 atm improves the dispersion stability of the metal fine particles, improves the storage stability and open time characteristics of the ink, improves the bending resistance, and reduces the volume resistivity. From the viewpoint, it is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, still more preferably 45 ° C. or higher, and preferably 150 ° C. or lower, more preferably 140 ° C. or lower, still more preferably 130 ° C. or lower, still more preferable. Is 100 ° C. or lower, more preferably 70 ° C. or lower. When two or more kinds of amine D are used, the boiling point of amine D is calculated as a weighted average value.
- amine D preferably contains a primary amine, more preferably contains a monoalkylamine, and more preferably n-propylamine, isopropylamine, n-butylamine, tert-butylamine, sec-butylamine and n-hexyl. It contains at least one selected from amines, more preferably at least one selected from n-propylamine and n-hexylamine, and even more preferably n-propylamine.
- the content of monoalkylamine in Amin D improves the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the volume resistance. From the viewpoint of reduction, it is 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 substantially 100% by mass.
- substantially 100% by mass means that components contained unintentionally may be contained. Examples of the component unintentionally contained include an amine D component other than the monoalkylamine contained in the amine as a raw material.
- the total content of n-propylamine, isopropylamine, n-butylamine, tert-butylamine, sec-butylamine and n-hexylamine in Amine D improves the dispersion stability of the metal fine particles and the storage stability of the ink.
- the content is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more. It is even more preferably 98% by mass or more, and even more preferably substantially 100% by mass.
- substantially 100% by mass means that components contained unintentionally may be contained.
- amine D when the total content of n-propylamine, isopropylamine, n-butylamine, tert-butylamine, sec-butylamine and n-hexylamine in amine D is substantially 100% by mass, it is unintentionally included.
- the component include amine D components other than the above-mentioned n-propylamine, isopropylamine, n-butylamine, tert-butylamine, sec-butylamine and n-hexylamine contained in the above-mentioned amine as a raw material.
- the total content of n-propylamine and n-hexylamine in Amine D improves the dispersion stability of the metal fine particles, and improves the storage stability and open time characteristics of the ink, and improves the bending resistance. From the viewpoint of reducing the volume resistance, 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 substantially. It is 100% by mass.
- substantially 100% by mass means that components contained unintentionally may be contained.
- the unintentionally contained component is the above-mentioned amine contained in the raw material.
- Amine D components other than n-propylamine and n-hexylamine can be mentioned.
- the ink of the present invention has a viewpoint of improving the dispersion stability of metal fine particles to improve the storage stability and open time characteristics of the ink, a viewpoint of improving bending resistance, a viewpoint of reducing volume resistivity, and a viewpoint of reducing the volume resistivity of the ink. From the viewpoint of improving handleability, it preferably contains diol E.
- the diol E can be used alone or in combination of two or more.
- the diol E is not particularly limited as long as it is a compound having two alcoholic hydroxyl groups in one molecule.
- diol C examples include ethylene glycol (boiling point 197 ° C.), propylene glycol (1,2-propanediol) (boiling point 188 ° C.), 1,2-butanediol (boiling point 193 ° C.), and 1,2-pentanediol (boiling point 206 ° C.).
- 1,2-Alcandiol such as 1,2-hexanediol (boiling point 223 ° C.); diethylene glycol (boiling point 245 ° C.), triethylene glycol (boiling point 287 ° C.), tetraethylene glycol (boiling point 314 ° C.), polyethylene glycol.
- Polyalkylene glycols such as dipropylene glycol (boiling point 232 ° C.), tripropylene glycol (boiling point 271 ° C.); 1,3-propanediol (boiling point 210 ° C.), 1,4-butanediol (boiling point 230 ° C.), 1, ⁇ , ⁇ -Alcandiol such as 5-pentindiol (boiling point 242 ° C.); 1,3-butanediol (boiling point 208 ° C.), 3-methyl-1,3-butanediol (boiling point 203 ° C.), 2-methyl- Examples thereof include 2,4-pentanediol (boiling point 196 ° C.).
- the boiling point of diol E at 1 atm improves the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the viewpoint of reducing the volume resistivity.
- the temperature is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, still more preferably 230 ° C. or lower, and even more preferably 200 ° C. or lower.
- the boiling point of diol E is calculated as a weighted average value.
- the diol E is preferably 1 from the viewpoint of improving the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the viewpoint of reducing the volume resistance.
- 2-Alkanediol containing at least one selected from polyalkylene glycol, more preferably containing 1,2-alkanediol, still more preferably containing at least one selected from propylene glycol and ethylene glycol, even more preferably. Contains propylene glycol.
- the content of 1,2-alkanediol in the diol E improves the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the volume resistance. From the viewpoint of reducing the rate and improving the handleability of the ink, it is 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, and more. More preferably, it is substantially 100% by mass.
- substantially 100% by mass means that components contained unintentionally may be contained.
- Examples of the component unintentionally contained include a diol E component other than the 1,2-alkanediol contained in the diol as a raw material.
- the total content of propylene glycol and ethylene glycol in the diol E improves the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the volume resistance. From the viewpoint of reducing the rate and improving the handleability of the ink, it is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, still more preferably 98% by mass or more, and more. More preferably, it is substantially 100% by mass.
- substantially 100% by mass means that components contained unintentionally may be contained.
- the component unintentionally contained include a diol E component other than the propylene glycol and ethylene glycol contained in the diol as a raw material.
- the ink of the present invention is preferable from the viewpoint of improving the dispersion stability of metal fine particles, improving the storage stability and open time characteristics of the ink, improving the bending resistance, and reducing the volume resistivity. Further contains water.
- the ink of the present invention has a fixing aid such as a dispersion of polymer particles, a moisturizing agent, a wetting agent, a penetrant, a surfactant, and a viscosity as other components other than the above-mentioned components as long as the effects of the present invention are not impaired. It may contain various additives such as a modifier, an antifoaming agent, an antiseptic, an antifungal agent, and an anticorrosive agent.
- the ink of the present invention is a method of adding and mixing a polymer B, a carboxylic acid C, an amine D, and if necessary, a diol E, water, etc. as a dispersant to metal fine particles A prepared in advance by a known method; a metal raw material compound. , A reducing agent, and a polymer B as a dispersant are mixed, and the metal raw material compound is reduced to obtain a dispersion of metal fine particles, and then carboxylic acid C, amine D, and if necessary, diol E, water, etc. Can be obtained by a method of adding and mixing.
- the polymer B is contained in advance from the viewpoint of improving the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the viewpoint of reducing the volume resistivity.
- a method of adding and mixing the carboxylic acid C, the amine D, and if necessary, diol, water and the like is preferable.
- the dry metal fine particle powder is obtained by mixing a metal raw material compound, a reducing agent, and polymer B, reducing the metal raw material compound with the reducing agent to obtain a dispersion of metal fine particles dispersed in the polymer B, and then obtaining the metal. It can be obtained by drying a dispersion of fine particles by freeze-drying or the like.
- the metal raw material compound is not particularly limited as long as it is a compound containing a metal constituting the above-mentioned metal fine particles A.
- the metal raw material compound include metal salts of inorganic acids or organic acids, metal oxides, metal hydroxides, metal sulfides, metal halides and the like, which contain the metal exemplified by the above-mentioned metal fine particles A.
- 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 one kind may be used alone or two or more kinds may be mixed and used.
- the metal raw material compound is preferably a metal salt of an inorganic acid or an organic acid, more preferably a metal salt of an inorganic acid, and further preferably a metal of nitric acid, from the viewpoint of versatility and productivity of metal fine particles. It is a salt, more preferably silver nitrate.
- the reducing agent is not particularly limited, and either an inorganic reducing agent or an organic reducing agent can be used, but an organic reducing agent is preferable.
- the organic reducing agent include 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 Alkanolamines such as n-propylamines, n-butylamines, n-hexylamines, diethylamines, dipropylamines, dimethylethylamines
- Alicyclic amines such as (poly) alkylene polyamines such as propylene triamine, triethylene tetramine and tetraethylene pentamine; alicyclic amines such as piperidine, pyrrolidine, N-methylpyrrolidin, morpholin; aniline, N-methylaniline, toluidine, Aromatic amines such as anicidine and phenetidine; aralkylamines such as benzylamine and N-methylbenzylamine can be mentioned.
- the inorganic reducing agent examples include borohydride salts such as sodium borohydride and ammonium borohydride; aluminum hydrides such as lithium borohydride 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 temperature of the reduction reaction is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 20 ° C. or higher, still more preferably 30 ° C. or higher, from the viewpoint of reducing the particle size of the metal fine particles and making them uniform. From the viewpoint of stably producing metal fine particles, the temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and even more preferably 50 ° C. or lower.
- the reduction reaction may be carried out in an air atmosphere or in an inert gas atmosphere such as nitrogen gas.
- the dispersion of the metal fine particles is purified before freeze-drying from the viewpoint of removing impurities such as the unreacted reducing agent and the excess dispersant B that does not contribute to the dispersion of the metal fine particles A.
- the method for purifying the dispersion of metal fine particles 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 molecular weight cut-off 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 more from the viewpoint of efficiently removing impurities. Below, it is more preferably 70,000 or less.
- the ink of the present invention can be obtained by further adding the above-mentioned various additives as needed and performing a filtration treatment with a filter or the like.
- the content of the metal fine particles A in the ink of the present invention is preferably 10% by mass or more, more preferably 15% by mass, from the viewpoint of reducing the volume resistance and improving the conductivity and improving the mirror surface gloss. % Or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and from the viewpoint of improving storage stability and open time characteristics, preferably 70% by mass or less, more preferably 60% by mass. Below, it is more preferably 50% by mass or less, still more preferably 40% by mass or less, still more preferably 35% by mass or less.
- the content of the polymer B in the ink of the present invention improves the dispersion stability of the metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving the bending resistance, and the volume resistance. From the viewpoint of reducing, preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, still more preferably 2% 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.
- the content of carboxylic acid C in the ink of the present invention improves the dispersion stability of metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving bending resistance, and the volume resistance. From the viewpoint of reducing the rate, it is 0.7% by mass or more, preferably 1% by mass or more, more preferably 1.5% by mass or more, still more preferably 2% by mass or more, still more preferably 2.5% by mass. As described above, it is more preferably 3% by mass or more, further preferably 4% by mass or more, and 15% by mass or less, preferably 10% by mass or less, and more preferably 7% by mass or less.
- the content of amine D in the ink of the present invention improves the dispersion stability of the metal fine particles, improves the storage stability and open time characteristics of the ink, improves the bending resistance, and has a mass resistance. From the viewpoint of reducing, it is 0.7% by mass or more, preferably 1% by mass or more, more preferably 1.5% by mass or more, still more preferably 2% by mass or more, still more preferably 3% by mass or more, and more. It is more preferably 4% by mass or more, further preferably 5% by mass or more, still more preferably 6% by mass or more, still more preferably 7% by mass or more, still more preferably 8% by mass or more, and 20% by mass. % Or less, preferably 17% by mass or less, more preferably 15% by mass or less, still more preferably 13% by mass or less, still more preferably 11% by mass or less.
- the mass ratio of the content of amine D to the content of carboxylic acid C in the ink of the present invention improves the dispersion stability of the metal fine particles, and the storage stability and open time of the ink. From the viewpoint of improving the characteristics, improving the bending resistance, and reducing the volume resistance, it is preferably 0.5 or more, more preferably 1 or more, still more preferably 1.5 or more, and preferably. Is 6 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, still more preferably 2.5 or less.
- the mass ratio of the content of amine D to the content of carboxylic acid C in the ink of the present invention is stable in dispersion of metal fine particles.
- it is preferably more than 1, more preferably 1.2 or more. It is more preferably 1.5 or more, and preferably 6 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, still more preferably 2.5 or less.
- the mass ratio [amine D / carboxylic acid C] is in the above range, the excess amine D that does not form a complex with the carboxylic acid C further interacts with the organic acid group of the polymer BI, and the dispersion stability of the metal fine particles is stable.
- the sex can be further improved.
- the equivalent ratio of amine D to carboxylic acid C in the ink of the present invention is a viewpoint of improving the dispersion stability of metal fine particles and improving the storage stability and open time characteristics of the ink. From the viewpoint of improving bending resistance and reducing the volume resistivity, it is preferably more than 1, more preferably 1.2 or more, still more preferably 1.4 or more, and preferably 5 or less, more preferably. Is 4 or less, more preferably 3 or less, still more preferably 2 or less, still more preferably 1.8 or less.
- the total content of the carboxylic acid C and the amine D in the ink of the present invention is a viewpoint of improving the dispersion stability of the metal fine particles, improving the storage stability and open time characteristics of the ink, and improving the bending resistance.
- % Or more more preferably 10% by mass or more, still more preferably 12% by mass or more, and preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, still more. It is preferably 20% by mass or less, and even more preferably 18% by mass or less.
- the mass ratio of the content of the polymer B to the total content of the metal fine particles A and the polymer B in the ink of the present invention improves the dispersion stability of the metal fine particles. From the viewpoint of improving the storage stability and open time characteristics of the ink, improving the bending resistance, and reducing the volume resistance, it is preferably 0.01 or more, more preferably 0.03 or more, still more preferably. It is 0.05 or more, and preferably 0.3 or less, more preferably 0.2 or less, still more preferably 0.1 or less.
- the mass ratio [polymer B / (metal fine particles A + polymer B)] is the mass of the metal fine particles A and the polymer B measured by the method described in Examples using a differential thermal weight simultaneous measurement device (TG / DTA). It is calculated from.
- the content of diol E in the ink of the present invention improves the dispersion stability of metal fine particles to improve the storage stability and open time characteristics of the ink, the viewpoint of improving bending resistance, and the volume resistance. From the viewpoint of reducing the amount of ink, it is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferable. Is 40% by mass or less.
- the content of water in the ink of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less. It is mass% or less, more preferably 30 mass% or less.
- the average particle size of the metal fine particles A contained in the ink of the present invention is from the viewpoint of storage stability and open time characteristics, from the viewpoint of reducing volume resistivity to improve conductivity, and from the viewpoint of improving mirror surface gloss. Therefore, it is preferably 3 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more, and preferably 100 nm or less, more preferably 70 nm or less, still more preferably 50 nm or less, still more preferably 40 nm or less, still more preferably. Is 30 nm or less.
- the average particle size of the metal fine particles A can be measured by the method described in Examples.
- the viscosity of the ink of the present invention at 30 ° C. is preferably 2 mPa ⁇ s or more, more preferably 3 mPa ⁇ s or more, still more preferably 4 mPa ⁇ s or more, still more preferably 5 mPa ⁇ s or more from the viewpoint of storage stability and open time characteristics.
- -S or more and 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.
- the viscosity of the ink is measured by the method described in Examples using an E-type viscometer.
- the pH of the ink of the present invention at 20 ° C. is preferably 7.0 or more, more preferably 7.2 or more, still more preferably 7.5 or more, from the viewpoint of storage stability and open time characteristics. 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 ink of the present invention can form a metal film having excellent storage stability and bending resistance in an environment of room temperature or higher, it is particularly suitable for inkjet printing, flexographic printing, gravure printing, screen printing, and offset printing. , Can be suitably used for various types of printing such as dispenser printing. Above all, the ink of the present invention is preferably used for inkjet printing because it has excellent open-time characteristics as described above.
- the ink of the present invention can be used in a wide range of applications because it can form a metal film having excellent storage stability and bending resistance in an environment of room temperature or higher.
- the applications include, for example, decorative materials for imparting mirror gloss; wiring materials used for forming conductive circuits, electrode materials, conductive materials such as multilayer ceramic capacitors (hereinafter, also referred to as “MLCC”); solder and the like. Bonding materials; various sensors; antennas such as automatic recognition technology (RFID (radio frequency identifier), hereinafter also referred to as "RFID”) tags using short-range wireless communication; catalysts; optical materials; medical materials and the like.
- RFID automatic recognition technology
- the ink of the present invention is preferably used for producing a printed matter on which a conductive circuit is formed.
- a method for producing a printed matter of the present invention a method of printing on a base material using the metal fine particle-containing ink to obtain a printed matter having a metal film formed on the base material is preferable. This makes it possible to obtain a printed matter on which a metal film having excellent conductivity, mirror gloss and the like is formed.
- a patterned metal film can be formed by forming a patterned printed image on a substrate, and this patterned metal film can be used as a conductive circuit. Can be done. That is, the method for producing a printed matter of the present invention is preferably used as a method for producing a printed matter in which a conductive circuit is formed on a base material. In the production of printed matter on which a conductive circuit is formed, the base material may be referred to as a "board".
- base material examples include paper; cloth; resin; metal; glass; ceramic or a composite material thereof.
- paper base material examples include coated paper (coated paper, art paper, etc.), uncoated paper, plain paper, kraft paper, synthetic paper, processed paper, paperboard, and the like.
- fabric used as the base material include natural fibers such as cotton, silk and linen, fabrics made of synthetic fibers such as rayon fibers, acetate fibers, nylon fibers and polyester fibers, and blended fabrics made of two or more of these fibers. Can be mentioned.
- the resin base material examples include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polypropylene (PP), polyamide (PA), polyimide (PI), polyvinyl chloride (PVC), and poly.
- Examples thereof include synthetic resin films such as methyl methacrylate (PMMA), polystyrene (PS), acrylic nitrile-butadiene-styrene copolymer (ABS), acrylic nitrile-styrene copolymer (AS), and polypropylene (PC).
- the metal base material examples include substrates using metals such as gold, silver, copper, palladium, platinum, aluminum, nickel, and tin.
- the base material is preferably at least one selected from a paper base material and a resin base material, and more preferably a paper base material, from the viewpoint of bending resistance.
- the base material may be a rigid base material or a flexible base material, but the metal fine particle-containing ink is a flexible base material from the viewpoint of being able to form a metal film having excellent bending resistance. Is preferable.
- the printing method of the metal fine particle-containing ink on the substrate various patterning printing methods such as inkjet printing, flexographic printing, gravure printing, screen printing, offset printing, and dispenser printing are preferably mentioned.
- a fine conductive circuit can be formed on the base material, and a design having excellent mirror surface design can be applied to the base material.
- the amount of the metal fine particle-containing ink applied to the substrate can be appropriately adjusted according to the size and type of the circuit or electrode to be formed, the desired degree of mirror gloss, and the design.
- the ink can be loaded into a known inkjet printing apparatus and ejected as ink droplets onto a substrate to form a printed image.
- the inkjet printing apparatus includes a thermal type and a piezo type, and it is more preferable to use the ink for thermal type inkjet printing.
- the head temperature of the inkjet head is preferably 15 ° C. or higher, more preferably 20 ° C. or higher, further preferably 25 ° C. or higher, and preferably 45 ° C. or lower, more preferably 40 ° C. or lower, still more preferably 35 ° C. or lower.
- the head voltage of the inkjet head is preferably 5 V or more, more preferably 10 V or more, still more preferably 15 V or more, and preferably 40 V or less, more preferably 35 V or less, still more preferably, from the viewpoint of printing efficiency and the like. 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 and the like. It is 35 kHz or less.
- the amount of ejected droplets of the ink according to the present invention is preferably 5 pL or more, more preferably 10 pL or more, and preferably 30 pL or less, more preferably 20 pL or less per drop.
- the amount of the ink according to the present invention applied to the substrate is preferably 0.5 g / m 2 or more, more preferably 1 g / m 2 or more, still more preferably 2 g / m 2 or more, and more preferably 2 g / m 2 or more as a solid content. It is preferably 20 g / m 2 or less, more preferably 15 g / m 2 or less, still more preferably 10 g / m 2 or less.
- the print 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” as used herein refers to the number of dots per inch (2.54 cm) formed on the substrate.
- “resolution is 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 a nozzle row is 600 dpi (dots / inch), the corresponding 1 A row of 600 dpi dots per inch is formed in a direction perpendicular to the transport direction of the substrate, and when the ink droplets are ejected while moving the substrate in the transport direction, the substrate is also 1 inch in the transport direction. It means that a row of dots of 600 dpi is formed per unit.
- 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 method for producing a printed matter of the present invention uses the ink on a substrate from the viewpoint of reducing volume resistivity to improve conductivity, improving mirror gloss, and improving bending resistance. After printing, it is preferable to perform a sintering process for sintering the metal fine particles A in the ink film on the substrate. By the sintering treatment, the ink solvent in the ink film is evaporated and dried, and the metal fine particles A are further sintered to form a conductive circuit made of a metal film having a low volume resistivity.
- the temperature of the sintering treatment is preferably lower than the temperature at which the base material is deformed, and specifically, from the viewpoint of reducing the resistivity of the metal film, under normal pressure, preferably 25 ° C. or higher, more preferably 50 ° C. or higher. It is more preferably 100 ° C. or higher, further preferably 120 ° C. or higher, still more preferably 140 ° C. or higher, and preferably 200 ° C. or lower, more preferably 180 ° C. or lower, still more preferably 160 ° C. or lower.
- the relative humidity of the surrounding environment of the sintering treatment is preferably 20% or more, more preferably 30% or more, further preferably 40% or more, and preferably 65% or less, more preferably 60% or less.
- the sintering treatment is carried out at a high temperature of 100 ° C. or higher and then stored at a low temperature for treatment.
- the low temperature treatment is preferably carried out 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 treatment temperature, but from the viewpoint of reducing the resistivity of the metal film, it is preferably 1 minute or longer, more preferably 5 minutes or longer, still more preferably 7. It is more than a minute, and from the viewpoint of productivity, it is preferably 6 hours or less, more preferably 3 hours or less, still more preferably 1 hour or less, still more preferably 30 minutes or less.
- the time of the low temperature treatment in the sintering treatment can be appropriately adjusted depending on the treatment temperature, but from the viewpoint of reducing the resistivity of the metal film, it is preferably 1 hour or more, more preferably 3 hours or more, still more preferably 6. It is more than an hour, more preferably 12 hours or more, and from the viewpoint of productivity, it is preferably 36 hours or less, more preferably 24 hours or less.
- the sintering treatment may be carried out under an air atmosphere or an inert gas atmosphere such as nitrogen gas, but when the substrate is a metal that is easily oxidized, it is under a nitrogen gas atmosphere. Is preferable.
- the method of the sintering treatment is not particularly limited, and is a method of heating by bringing a heater into contact with the surface of the base material opposite to the surface on which the ink film is formed; by applying hot air to the ink film surface on the base material.
- Method of heating Method of heating; Method of heating by bringing a heater close to the ink film surface on the substrate; Method of storing the substrate on which the ink film is formed in a constant temperature device that can keep the temperature constant;
- a method of heating by steam curing using high-temperature steam a method of heating by irradiation with light such as near-infrared light and ultraviolet light can be mentioned.
- the volume resistivity ⁇ v of the metal film formed by the production method of the present invention is preferably 10 ⁇ ⁇ cm or less, more preferably 7 ⁇ ⁇ cm or less, still more preferably 4 ⁇ ⁇ cm or less, and the printability is easy to produce. From the viewpoint of the above, it is preferably 2 ⁇ ⁇ cm or more, more preferably 2.5 ⁇ ⁇ cm or more, still more preferably 3 ⁇ ⁇ cm or more.
- the volume resistivity ⁇ v can be measured by the method described in Examples.
- the printed matter obtained by the production method of the present invention has low volume resistivity and excellent bending resistance, it can be used in various electronic and electrical devices as a conductive composite material including a base material and a conductive circuit.
- the conductive composite material is an RFID tag; a capacitor such as MLCC; an LTCC substrate; an electronic paper; an image display device such as a liquid crystal display, an organic EL display, a touch panel; an organic EL element; an organic transistor; a printed wiring board, a flexible wiring board.
- Wiring boards such as; organic solar cells; flexible batteries; can be used for various devices such as sensors such as flexible sensors.
- a metal fine particle-containing ink containing metal fine particles A, carboxylic acid C, and amine D dispersed in polymer B has at least one selected from organic acid groups and organic base groups.
- Carboxylic acid C has 1 or more and 6 or less carbon atoms.
- Amine D has 1 or more and 6 or less carbon atoms.
- the content of carboxylic acid C is 0.7% by mass or more and 15% by mass or less.
- Polymer B has at least one selected from organic acid groups and organic base groups.
- Carboxylic acid C has 1 or more and 6 or less carbon atoms.
- Amine D has 1 or more and 6 or less carbon atoms.
- the content of carboxylic acid C is 0.7% by mass or more and 15% by mass or less.
- the content of amine D is 0.7% by mass or more and 20% by mass or less.
- Polymer B contains at least one selected from a carboxy group and an imino group.
- Carboxylic acid C contains a monocarboxylic acid and Amine D contains a primary amine
- Polymer B has at least one selected from organic acid groups and organic base groups.
- Carboxylic acid C has 1 or more and 6 or less carbon atoms.
- Amine D has 1 or more and 6 or less carbon atoms.
- the content of carboxylic acid C is 0.7% by mass or more and 15% by mass or less.
- the content of amine D is 0.7% by mass or more and 20% by mass or less.
- the polymer B is derived from a structural unit derived from at least one selected from (meth) acrylic acid and maleic acid as the monomer (b-1) and from at least one selected from styrene and a styrene derivative as the monomer (b-2). Containing at least one selected from vinyl polymers and polyethyleneimines, including constituent units, Carboxylic acid C comprises at least one selected from formic acid, acetic acid, propionic acid, fatty acid, isobutanoic acid, hexanoic acid, glyoxylic acid and lactic acid.
- Amine D contains a monoalkylamine, The metal fine particle-containing ink according to ⁇ 1> or ⁇ 2>, wherein the metal constituting the metal fine particles A contains at least one selected from silver, copper and nickel.
- Polymer B has at least one selected from organic acid groups and organic base groups.
- Carboxylic acid C has 1 or more and 6 or less carbon atoms.
- Amine D has 1 or more and 6 or less carbon atoms.
- the content of carboxylic acid C is 0.7% by mass or more and 15% by mass or less.
- the content of amine D is 0.7% by mass or more and 20% by mass or less.
- the polymer B is derived from a structural unit derived from at least one selected from (meth) acrylic acid and maleic acid as the monomer (b-1) and from at least one selected from styrene and a styrene derivative as the monomer (b-2).
- a vinyl polymer containing a structural unit and a structural unit derived from alkoxypolyethylene glycol (meth) acrylate as the monomer (b-3) is contained.
- Carboxylic acid C comprises at least one selected from formic acid, acetic acid, fatty acid, hexane acid and glyoxylic acid.
- Amine D comprises at least one selected from n-propylamine, isopropylamine, n-butylamine, tert-butylamine, sec-butylamine and n-hexylamine.
- the metal fine particle-containing ink according to any one of ⁇ 1> to ⁇ 3>, wherein the metal constituting the metal fine particles A contains at least one selected from silver, copper and nickel.
- Polymer B has at least one selected from organic acid groups and organic base groups.
- Carboxylic acid C has 1 or more and 6 or less carbon atoms.
- Amine D has 1 or more and 6 or less carbon atoms.
- the content of carboxylic acid C is 0.7% by mass or more and 15% by mass or less.
- the content of amine D is 0.7% by mass or more and 20% by mass or less.
- Polymer B contains 0.5% by mass or more and 20% by mass or less of a structural unit derived from at least one selected from (meth) acrylic acid and maleic acid as the monomer (b-1), and styrene and styrene as the monomer (b-2).
- the structural unit derived from at least one selected from the styrene derivative is 30% by mass or more and 90% by mass or less, and the structural unit derived from alkoxypolyethylene glycol (meth) acrylate as the monomer (b-3) is 5% by mass or more and 50% by mass or less.
- Carboxylic acid C comprises at least one selected from formic acid, caproic acid and glyoxylic acid.
- Amine D contains at least one selected from n-propylamine and n-hexylamine, and contains.
- the metal fine particle-containing ink according to any one of ⁇ 1> to ⁇ 4>, wherein the metal constituting the metal fine particles A contains at least one selected from silver, copper and nickel.
- ⁇ 6> A metal fine particle-containing ink containing metal fine particles A, carboxylic acid C, and amine D dispersed in polymer B.
- Polymer B has at least one selected from organic acid groups and organic base groups.
- Carboxylic acid C has 1 or more and 6 or less carbon atoms.
- Amine D has 1 or more and 6 or less carbon atoms.
- the content of carboxylic acid C is 0.7% by mass or more and 15% by mass or less.
- the content of amine D is 0.7% by mass or more and 20% by mass or less.
- Polymer B contains 0.5% by mass or more and 20% by mass or less of a structural unit derived from at least one selected from (meth) acrylic acid and maleic acid as the monomer (b-1), and styrene and styrene as the monomer (b-2).
- the structural unit derived from at least one selected from the styrene derivative is 30% by mass or more and 70% by mass or less, and the structural unit derived from alkoxypolyethylene glycol (meth) acrylate as the monomer (b-3) is 20% by mass or more and 50% by mass or less.
- Carboxylic acid C comprises at least one selected from formic acid and glyoxylic acid.
- Amine D contains n-propylamine, The metal fine particle-containing ink according to any one of ⁇ 1> to ⁇ 5>, wherein the metal constituting the metal fine particles A contains silver.
- ⁇ 7> Any of ⁇ 1> to ⁇ 6>, wherein the mass ratio [amine D / carboxylic acid C] of the content of amine D to the content of carboxylic acid C in the metal fine particle-containing ink is 0.5 or more and 6 or less.
- the mass ratio [amine D / carboxylic acid C] of the content of amine D to the content of carboxylic acid C in the metal fine particle-containing ink is 0.5 or more and 6 or less.
- the content of the metal fine particles A in the metal fine particle-containing ink is 10% by mass or more and 70% by mass or less
- the content of the polymer B is 0.5% by mass or more and 10% by mass or less.
- the metal fine particle-containing ink according to any one of the above.
- ⁇ 9> The metal fine particle-containing ink according to any one of ⁇ 1> to ⁇ 8>, wherein the metal fine particle-containing ink contains diol E.
- ⁇ 10> The metal fine particle-containing ink according to ⁇ 9>, wherein the content of the diol E in the metal fine particle-containing ink is 5% by mass or more and 60% by mass or less.
- ⁇ 11> The metal fine particle-containing ink according to any one of ⁇ 1> to ⁇ 10>, which has a viscosity at 30 ° C. of 2 mPa ⁇ s or more and 50 mPa ⁇ s or less.
- ⁇ 12> The metal fine particle-containing ink according to any one of ⁇ 1> to ⁇ 11>, which is used for inkjet printing.
- ⁇ 13> A method for producing a printed matter, which comprises printing on a substrate using the metal fine particle-containing ink according to any one of ⁇ 1> to ⁇ 12> to obtain a printed matter in which a conductive circuit is formed on the substrate.
- TSKgel SuperAWM-H TSKgel SuperAW3000, TSKgel guardcolumn Super AW-H
- flow velocity 0.5 mL / min
- PStQuickB monodisperse polystyrene kit
- PStQuick C F-288, F-40, F-4, A-5000, A-500
- the measurement sample was prepared by mixing 0.1 g of polymer BI in a glass vial with 10 mL of the eluent, stirring at 25 ° C. for 10 hours with a magnetic stirrer, and using a syringe filter (DISMIC-13HP PTFE 0.2 ⁇ m, Advantech Toyo Co., Ltd.). The one filtered with (manufactured by) was used.
- the particle size was measured by a dynamic light scattering method using a laser particle analysis system "ELS-8000" (manufactured by Otsuka Electronics Co., Ltd.), and calculated by a cumulant method analysis.
- the measurement conditions were a temperature of 25 ° C., an angle between the incident light and the detector of 90 °, and the number of integrations was 100 times, and the refractive index of water (1.333) was input as the refractive index of the dispersion solvent.
- For the measurement sample weigh the sample into a screw tube (No. 5 manufactured by Marum Co., Ltd.), add water so that the solid content concentration becomes 5 ⁇ 10 -3 % by mass, and use a magnetic stirrer at 25 ° C. The one stirred for 1 hour was used.
- Preparation Example 1 (Preparation of Polymer BI-1) Put 100 g of 1,4-dioxane in a 1000 mL four-necked round-bottom flask equipped with a thermometer, two dropping funnels with 100 mL nitrogen bypass, and a reflux device, and heat the internal temperature of the flask to 80 ° C with an oil bath. After that, nitrogen bubbling was performed for 10 minutes. Next, as a raw material monomer for polymer BI, 98% acrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) 3 g, methoxypolyethylene glycol (EO9 mol) acrylate (manufactured by Shin-Nakamura Chemical Industries, Ltd.
- NK ester AM-90G 37 g, 60 g of styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) and 1.5 g of 3-mercaptopropionic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) are dissolved in a polybeaker. And put it in the dropping funnel (1).
- Preparation Example 2 (Preparation of Polymer BI-2)
- polymer BI-2 polyacrylic acid, acid value: 780 mgKOH / g, Mn: 7,700
- the raw material monomer of the polymer BI was changed to only 100 g of 98% acrylic acid. Obtained.
- Preparation Example 3 (Preparation of Polymer BI-3) Polymer BI-3 (acrylic acid / methoxypolyethylene) was prepared in the same manner except that the raw material monomers of the polymer BI were changed to 3 g of 98% acrylic acid, 17 g of methoxypolyethylene glycol (EO9 mol) acrylate, and 80 g of styrene in Preparation Example 1. Glycol (EO9 mol) acrylate / styrene copolymer, acid value: 23 mgKOH / g, Mn: 7,500) was obtained.
- Preparation Example 4 (Preparation of Polymer BI-4)
- polymer BI-4 (acrylic acid / styrene copolymer, acid value: 23 mgKOH / g, Mn) was similarly used except that the raw material monomers of the polymer BI were changed to 3 g of 98% acrylic acid and 97 g of styrene. : 5,900) was obtained.
- Preparation Example 5 (Preparation of Polymer BII-1) Polyethylenimine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., reagent, weight average molecular weight of about 10,000) was used as the polymer BII, and a vacuum dryer "VO420" (manufactured by Advantech Toyo Co., Ltd.) was used. The polymer BII-1 was obtained by drying in.
- Example 1 [Manufacturing of dry metal fine particles]
- Step 1 In a 1000 mL glass beaker, 23 g of N, N-dimethylethanolamine (hereinafter, also referred to as “DMAE”) was put as a reducing agent, and the mixture was heated to 40 ° C. in an oil bath while stirring with a magnetic stirrer.
- DMAE N, N-dimethylethanolamine
- Step 2 put 140 g of silver nitrate as a metal raw material compound, 8 g of polymer BI-1 as a dispersant, and 70 g of ion-exchanged water into a 100 mL beaker, and stir at 40 ° C. using a magnetic stirrer until it becomes visually transparent. , A mixed solution was obtained.
- the obtained mixed solution was placed in a 1000 mL dropping funnel, and the mixed solution was added dropwise to DMAE kept at 40 ° C. over 30 minutes. Then, the reaction solution was stirred in an oil bath for 5 hours while controlling the temperature of the reaction solution to 40 ° C., and then air-cooled to obtain a dark brown dispersion containing dispersed silver fine particles.
- This tube was immersed in 5 L of ion-exchanged water in a 5 L glass beaker, and the water temperature was maintained at 20 to 25 ° C. and the mixture was stirred for 1 hour. After that, the work of exchanging the entire amount of ion-exchanged water every hour was repeated three times, sampling was performed every hour, and the method using the differential thermal weight simultaneous measurement device (TG / DTA) described in (2) above.
- TG / DTA differential thermal weight simultaneous measurement device
- Step 3 The purified dispersion obtained in step 2 was used in a freeze-dryer (manufactured by Tokyo Rika Kikai Co., Ltd., model: FDU-2110) attached with a dry chamber (manufactured by Tokyo Rika Kikai Co., Ltd., model: DRC-1000). Then, the metal fine particle dry powder 1 was obtained by freeze-drying under the drying conditions (freezing at ⁇ 25 ° C. for 1 hour, decompression at ⁇ 10 ° C. for 9 hours, depressurization at 25 ° C. for 5 hours, decompression degree 5 Pa).
- the inkjet printer is used as a base material on a commercially available paper substrate "PowerCoat XD 200" (manufactured by Arjoggings, thickness 200 ⁇ m) with a width of 204 mm and a length of 275 mm.
- printing conditions paper type: photo glossy paper, mode setting: clean, grayscale.
- the paper substrate on which the ink film was formed was heated on a hot stage at 150 ° C. for 60 minutes, then stored for 24 hours in an environment with a temperature of 25 ° C. and a relative humidity of 55%, sintered, and placed on the paper substrate.
- a printed matter on which a metal film was formed was obtained. The obtained printed matter was evaluated by the following method.
- Example 2 In the production of the ink of Example 1, a metal fine particle-containing ink and a printed matter were obtained in the same manner except that the type of the carboxylic acid C or the amine D or the composition of the ink was changed according to Table 1.
- Example 8 to 11 Comparative Example 1
- dry metal fine particle powders 2 to 5,51 were obtained in the same manner except that the types of the dispersants were changed as shown in Table 1.
- the metal fine particle dry powder 1 instead of the metal fine particle dry powder 1, the metal fine particle dry powders 2 to 5,51 were used, respectively, to obtain metal fine particle-containing ink and printed matter.
- thioapple acid manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent
- Example 19 In step 1 in the production of the dry metal fine particle powder of Example 1, 140 g of copper sulfate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade) was added as a metal raw material compound in a 1000 mL glass beaker, and polymer B1-1 was used as a dispersant. 8 g and 70 g of ion-exchanged water were added, and the mixture was stirred at 40 ° C. using a magnetic stirrer until it became visually transparent. The mixture was heated to 40 ° C. in an oil bath while stirring with a magnetic stirrer.
- copper sulfate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade
- Example 1 25 g of hydrazine monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., special grade) as a reducing agent was added to a 100 mL dropping funnel, and the mixture was added dropwise to the glass beaker over 3 hours. Then, the reaction solution was stirred in an oil bath for 5 hours while controlling the temperature of the reaction solution to 40 ° C., and then air-cooled to obtain a dispersion containing dispersed copper fine particles. After that, the metal fine particle dry powder 6 was obtained in the same manner as in Step 2 and Step 3 of Example 1. Next, in Example 1, the metal fine particle dry powder 6 was used instead of the metal fine particle dry powder 1, to obtain an ink containing metal fine particles and a printed matter.
- hydrazine monohydrate manufactured by Wako Pure Chemical Industries, Ltd., special grade
- Example 20 Metal fine particle dry powder 7 in the same manner except that copper sulfate was changed to anhydrous nickel chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., reagent) as the metal raw material compound in step 1 in the production of the metal fine particle dry powder of Example 19.
- the metal fine particle dry powder 7 was used instead of the metal fine particle dry powder 1, to obtain an ink containing metal fine particles and a printed matter.
- the inks of Examples 1 to 22 are superior in storage stability and open time characteristics as compared with Comparative Examples 1 to 7, and the minimum diameter of the cylindrical mandrel in which cracks did not occur is also small. It can be seen that a metal film having excellent bending resistance can be formed. Further, it can be seen that the inks of Examples 1 to 22 can form a metal film having a lower volume resistivity as compared with Comparative Examples 1 to 7.
- the present invention it is possible to obtain an ink containing metal fine particles having excellent storage stability even in an environment of room temperature or higher, and having excellent open-time characteristics when used for inkjet printing, and a metal having excellent bending resistance.
- a printed matter on which a film is formed can be obtained. Therefore, the metal fine particle-containing ink of the present invention and the method for producing a printed matter using the ink can be suitably used for conductive applications in printed electronics and decorative applications for imparting mirror gloss.
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Abstract
Description
例えば、特開2009-74171号(特許文献1)では、粗大粒子が少なく、高濃度で金属ナノ粒子を含む長期間の保存安定性に優れた金属コロイド粒子の提供を目的として、金属ナノ粒子と、この金属ナノ粒子を被覆する保護コロイドとで構成された金属コロイド粒子であって、前記保護コロイドが、カルボキシル基を有する有機化合物と、高分子分散剤とで構成されている金属コロイド粒子及び溶媒を含む分散液等が記載されている。
ポリマーBが、有機酸基及び有機塩基基から選ばれる少なくとも1種を有し、
カルボン酸Cの炭素数が、1以上6以下であり、
アミンDの炭素数が、1以上6以下であり、
カルボン酸Cの含有量が、0.7質量%以上15質量%以下であり、
アミンDの含有量が、0.7質量%以上20質量%以下である、金属微粒子含有インクに関する。
また、金属微粒子を含有するインクは、該金属微粒子の分散安定性から冷蔵保存を余儀なくされるため、該インクを用いる際の作業性が損なわれる場合があり、常温(25℃)以上の環境下においても保存安定性に優れることが求められている。
しかしながら、特許文献1の技術では、保存安定性及び耐折り曲げ性が十分でないことが判明した。
本発明は、保存安定性に優れ、かつ耐折り曲げ性に優れる印刷物を得ることができる金属微粒子含有インク、及び該インクを用いる印刷物の製造方法に関する。
すなわち、本発明は、次の[1]及び[2]に関する。
[1]ポリマーBで分散されてなる金属微粒子A、カルボン酸C、及びアミンDを含有する金属微粒子含有インクであって、
ポリマーBが、有機酸基及び有機塩基基から選ばれる少なくとも1種を有し、
カルボン酸Cの炭素数が、1以上6以下であり、
アミンDの炭素数が、1以上6以下であり、
カルボン酸Cの含有量が、0.7質量%以上15質量%以下であり、
アミンDの含有量が、0.7質量%以上20質量%以下である、金属微粒子含有インク。
[2]前記[1]に記載の金属微粒子含有インクを用いて基材に印刷し、該基材に導電回路が形成された印刷物を得る、印刷物の製造方法。
本発明の金属微粒子含有インクは、ポリマーBで分散されてなる金属微粒子A、カルボン酸C、及びアミンDを含有する金属微粒子含有インクであって、ポリマーBが、有機酸基及び有機塩基基から選ばれる少なくとも1種を有し、カルボン酸Cの炭素数が、1以上6以下であり、アミンDの炭素数が、1以上6以下であり、カルボン酸Cの含有量が、0.7質量%以上15質量%以下であり、アミンDの含有量が、0.7質量%以上20質量%以下である。
本発明のインクに含まれる金属微粒子は、有機酸基及び有機塩基基から選ばれる少なくとも1種を有するポリマーで分散されており、金属微粒子の分散安定性が向上すると考えらえる。さらに、炭素数が所定の範囲である低分子カルボン酸及び低分子アミンをそれぞれ所定の割合で含有するため、該ポリマー、該低分子カルボン酸、及び該低分子アミン間の相互作用により金属微粒子の分散安定性が向上すると考えられる。その結果、これらの金属微粒子の分散安定性に対する相乗効果により、保存安定性が向上すると考えられる。
また、金属微粒子含有インクを用いて印刷した後、インクの乾燥過程において金属微粒子を分散しているポリマーが低分子カルボン酸及び低分子アミンで置換され、さらに低分子カルボン酸及び低分子アミンは、複合体を形成して疑似的に高沸点化合物のような機能を発揮し、インク溶媒の揮発性を低下させるため、徐々にインク溶媒がインク被膜から揮発することにより金属微粒子が再配列する猶予を与えることとなり、緻密な金属膜が作成された印刷物を得ることができ、印刷物の耐折り曲げ性が向上すると考えられる。特に、本発明のインクを導電用途として用いる場合には、この緻密な金属膜の形成により体積抵抗率を低減することができる。
また、印刷方法としてインクジェット印刷を用いる場合には、印刷の信頼性の指標として、所定の時間の印刷休止後に印刷を再開した際においてもインクを良好に吐出することができるオープンタイム特性の向上も求められている。本発明のインクは、前述のとおり、金属微粒子の分散安定性の向上と共に、低分子カルボン酸及び低分子アミンから形成される複合体が疑似的に高沸点化合物のような機能を発揮し、インクジェットヘッドのノズル近傍でのインクの乾燥が抑制されて、オープンタイム特性も向上すると考えられる。
以上のとおり、本組成によれば、金属微粒子含有インクの保存安定性及びインクジェット印刷におけるオープンタイム特性と印刷物の耐折り曲げ性とを高度に両立させることができる。
金属微粒子Aを構成する金属(金属原子)は、チタン、ジルコニウム等の第4族の遷移金属、バナジウム、ニオブ等の第5族の遷移金属、クロム、モリブデン、タングステン等の第6族の遷移金属、マンガン、テクネチウム、レニウム等の第7族の遷移金属、鉄、ルテニウム等の第8族の遷移金属、コバルト、ロジウム、イリジウム等の第9族の遷移金属、ニッケル、パラジウム、白金等の第10族の遷移金属、銅、銀、金等の第11族の遷移金属、亜鉛、カドミウム等の第12族の遷移金属、アルミニウム、ガリウム、インジウム等の第13族の金属、ゲルマニウム、スズ、鉛等の第14族の金属などが挙げられる。金属微粒子Aを構成する金属は、1種を単独金属として用いてもよく、2種以上を併用して合金として用いてもよい。中でも、導電性の観点、加飾性の観点、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点から、金属微粒子Aを構成する金属は、好ましくは第4族~第11族で第4周期~第6周期の遷移金属を含み、より好ましくは銅、ニッケルや金、銀、白金、パラジウム等の貴金属を含み、更に好ましくは金、銀、銅、ニッケル、及びパラジウムから選ばれる少なくとも1種を含み、より更に好ましくは金、銀、銅及びニッケルから選ばれる少なくとも1種を含み、より更に好ましくは銀、銅及びニッケルから選ばれる少なくとも1種を含み、より更に好ましくは銀を含み、より更に好ましくは銀である。金属の種類は、高周波誘導結合プラズマ発光分析法により確認することができる。
金属微粒子A中の銀、銅及びニッケルの合計含有量は、導電性の観点、加飾性の観点、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点から、好ましくは80質量%以上、より好ましくは90質量%以上、更に好ましくは95質量%以上、より更に好ましくは98質量%以上、より更に好ましくは実質的に100質量%である。
金属微粒子A中の銀の含有量は、導電性の観点、加飾性の観点、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点から、好ましくは80質量%以上、より好ましくは90質量%以上、更に好ましくは95質量%以上、より更に好ましくは98質量%以上、より更に好ましくは実質的に100質量%である。
ここで「実質的100質量%」とは、意図せずに含まれる成分を含みうることを意味する。意図せずに含まれる成分としては、例えば、不可避的不純物が挙げられる。
本発明に係る金属微粒子Aは、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、ポリマーBで分散されてなる。ポリマーBは、有機酸基及び有機塩基基から選ばれる少なくとも1種を有する。
有機酸基としては、カルボキシ基(-COOM)、スルホン酸基(-SO3M)、リン酸基(-OPO3M2)等の解離して水素イオンが放出されることにより酸性を呈する基、又はそれらの解離したイオン形(-COO-、-SO3 -、-OPO3 2-、-OPO3 -M)等が挙げられる。ここで、Mは、水素原子、アルカリ金属、アンモニウム又は有機アンモニウムを示す。これらの中でも、有機酸基は、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくはカルボキシ基である。
有機塩基基としては、第一級アミノ基(-NH2)、第二級アミノ基(-NHR1、=NH(イミノ基))、第三級アミノ基-NR1R2、第四級アンモニウム基(-N+R1R2R3)等が挙げられる。ここで、R1~R3は、メチル基、エチル基、プロピル基、イソプロピル基、ヒドロキシメチル基、又はヒドロキシエチル基を示す。これらの中でも、有機塩基基は、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくは第二級アミノ基であり、より好ましくはイミノ基である。
ポリマーBは、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくはカルボキシ基及びイミノ基から選ばれる少なくとも1種を含み、より好ましくはカルボキシ基を含む。
ポリマーBは、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくは水溶性であり、より好ましくは水溶性の有機酸基を有するポリマーBI及び有機塩基基を有するポリマーBIIから選ばれる少なくとも1種であり、更に好ましくは水溶性の有機酸基を有するポリマーBIである。
本発明において、ポリマーBの「水溶性」とは、105℃で2時間乾燥させ、恒量に達したポリマーを、25℃の水100gに溶解させたときに、その溶解量が10g以上であり、好ましくは10g超であることを意味する。ポリマーBの溶解量は、例えば、ポリマーBIの場合には、ポリマーBIの有機酸基を水酸化ナトリウムで100%中和した時の溶解量であり、また、ポリマーBIIの場合には、ポリマーBIIの有機塩基基を塩酸で100%中和した時の溶解量である。
ポリマーBIは、有機酸基を有する。有機酸基の例は、先に例示したものと同様である。中でも、ポリマーBIの有機酸基は、好ましくはカルボキシ基である。
ポリマーBIの基本構造としては、アクリル系樹脂、スチレン系樹脂、スチレン-アクリル系樹脂、アクリルシリコーン系樹脂等のビニル系ポリマー;ポリエステル、ポリウレタン等の縮合系ポリマー等が挙げられる。中でも、ポリマーBIは、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、カルボキシ基を有するモノマー(b-1)由来の構成単位を含むビニル系ポリマーが好ましい。
前記ビニル系ポリマーは、好ましくはモノマー(b-1)由来の構成単位からなる単独重合体、又はモノマー(b-1)由来の構成単位と該モノマー(b-1)以外の他のモノマー由来の構成単位を含む共重合体である。前記ビニル系ポリマーが共重合体である場合、該ビニル系ポリマーは、ブロック共重合体、ランダム共重合体、交互共重合体のいずれでもよい。
モノマー(b-1)としては、(メタ)アクリル酸、クロトン酸、2-メタクリロイルオキシメチルコハク酸等の不飽和モノカルボン酸;マレイン酸、イタコン酸、フマル酸、シトラコン酸等の不飽和ジカルボン酸などが挙げられる。なお、前記不飽和ジカルボン酸は無水物であってもよい。
モノマー(b-1)は、1種を単独で又は2種以上を併用して用いてもよい。
モノマー(b-1)は、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくは(メタ)アクリル酸及びマレイン酸から選ばれる少なくとも1種であり、より好ましくは(メタ)アクリル酸である。
本明細書において、「(メタ)アクリル酸」とは、アクリル酸及びメタクリル酸から選ばれる少なくとも1種を意味する。以下における「(メタ)アクリル酸」も同義である。
ポリマーBIは、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくはカルボキシ基を有するモノマー(b-1)由来の構成単位と疎水性モノマー(b-2)由来の構成単位とを含むビニル系ポリマーである。
本明細書において「疎水性モノマー」とは、モノマーを25℃のイオン交換水100gへ飽和するまで溶解させたときに、その溶解量が10g未満であることをいう。モノマー(b-2)の前記溶解量は、前記と同様の観点から、好ましくは5g以下、より好ましくは1g以下である。
モノマー(b-2)は、スチレン系モノマー、(メタ)アクリル酸エステル等が挙げられる。
芳香族基含有(メタ)アクリル酸エステルとしては、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、フェニル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート等が好ましく、ベンジル(メタ)アクリレートがより好ましい。
脂肪族アルコール由来の炭化水素基を有する(メタ)アクリル酸エステルとしては、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくは炭素数1以上22以下の脂肪族アルコール由来の炭化水素基を有するものである。例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、オクチル(メタ)アクリレート、デシル(メタ)アクリレート、ドデシル(メタ)アクリレート、ステアリル(メタ)アクリレート等の直鎖アルキル基を有する(メタ)アクリレート;イソプロピル(メタ)アクリレート、イソブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、イソペンチル(メタ)アクリレート、イソオクチル(メタ)アクリレート、イソデシル(メタ)アクリレート、イソドデシル(メタ)アクリレート、イソステアリル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート等の分岐鎖アルキル基を有する(メタ)アクリレート;シクロヘキシル(メタ)アクリレート等の脂環式アルキル基を有する(メタ)アクリレート等が挙げられる。これらの中でも、脂肪族アルコール由来の炭化水素基を有する(メタ)アクリル酸エステルとしては、より好ましくは炭素数6以上10以下のアルキル基を有するものである。
モノマー(b-2)は、1種を単独で又は2種以上を併用して用いてもよい。
本明細書において、「(メタ)アクリレート」とはアクリレート及びメタクリレートから選ばれる少なくとも1種である。以下における「(メタ)アクリレート」も同義である。
ポリマーBがポリアルキレングリコール鎖を有する場合、ポリマーBIは、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくはポリオキシアルキレン基を有するモノマー(b-3)由来の構成単位を更に含むビニル系ポリマーである。
モノマー(b-3)としては、ポリアルキレングリコール(メタ)アクリレート、アルコキシポリアルキレングリコール(メタ)アクリレート、フェノキシポリアルキレングリコール(メタ)アクリレート等が挙げられる。モノマー(b-3)は、1種を単独で又は2種以上を併用して用いてもよい。
該アルコキシポリアルキレングリコール(メタ)アクリレートとしては、メトキシポリアルキレングリコール(メタ)アクリレート、エトキシポリアルキレングリコール(メタ)アクリレート、プロポキシポリアルキレングリコール(メタ)アクリレート、ブトキシポリアルキレングリコール(メタ)アクリレート、オクトキシポリアルキレングリコール(メタ)アクリレート等が挙げられる。
前記ポリオキシアルキレン基中のアルキレンオキシド由来の単位数は、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくは2以上、より好ましくは5以上、更に好ましくは7以上であり、そして、好ましくは100以下、より好ましくは70以下、更に好ましくは50以下、より更に好ましくは40以下、より更に好ましくは30以下、より更に好ましくは20以下である。
前記ポリオキシアルキレン基は、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、エチレンオキシド由来の単位とプロピレンオキシド由来の単位を含む共重合体であってもよい。エチレンオキシド由来の単位(EO)とプロピレンオキシド由来の単位(PO)とのモル比[EO/PO]は、好ましくは60/40以上、より好ましくは65/35以上、更に好ましくは70/30以上であり、そして、好ましくは90/10以下、より好ましくは85/15以下、更に好ましくは80/20以下である。
エチレンオキシド由来の単位とプロピレンオキシド由来の単位を含む共重合体は、ブロック共重合体、ランダム共重合体、交互共重合体のいずれであってもよい。
ポリマーBIが、モノマー(b-1)由来の構成単位とモノマー(b-2)由来の構成単位とを含むビニル系ポリマーである場合、ポリマーBI製造時における、原料モノマー中における各モノマーの含有量(未中和量としての含有量。以下同じ)又はポリマーBI中における各モノマー由来の構成単位の含有量は、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、次のとおりである。
モノマー(b-1)の含有量は、好ましくは0.5質量%以上、より好ましくは1質量%以上、更に好ましくは2質量%以上であり、そして、好ましくは20質量%以下、より好ましくは10質量%以下、更に好ましくは5質量%以下である。
モノマー(b-2)の含有量は、好ましくは30質量%以上、より好ましくは40質量%以上、更に好ましくは50質量%以上であり、そして、好ましくは98質量%以下、より好ましくは90質量%以下、更に好ましくは80質量%以下、より更に好ましくは70質量%以下である。
モノマー(b-1)とモノマー(b-2)の質量比[モノマー(b-1)/モノマー(b-2)]は、好ましくは0.01以上、より好ましくは0.02以上、更に好ましくは0.03以上、より更に好ましくは0.04以上であり、そして、好ましくは1以下、より好ましくは0.5以下、更に好ましくは0.1以下、より更に好ましくは0.07以下、より更に好ましくは0.05以下である。
ポリマーBIが、モノマー(b-1)由来の構成単位及びモノマー(b-2)由来の構成単位に加えて、更にモノマー(b-3)由来の構成単位を含むビニル系ポリマーである場合、ポリマーBI製造時における、原料モノマー中におけるモノマー(b-3)の含有量又はポリマーBI中におけるモノマー(b-3)由来の構成単位の含有量は、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくは5質量%以上、より好ましくは10質量%以上、更に好ましくは15質量%以上、より更に好ましくは20質量%以上、より更に好ましくは25質量%以上であり、そして、好ましくは50質量%以下、より好ましくは45質量%以下、更に好ましくは40質量%以下である。
ポリマーBIは、公知の方法で合成したものを用いてよく、市販品を用いてもよい。ポリマーBIの市販品としては、BYK社製のDISPERBYK-190、同2015等が挙げられる。
さらに、ポリマーBIとしては、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点から、低温焼結性及び低温接合性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくは、(b-1)由来の構成単位が0.5質量%以上20質量%以下、(b-2)由来の構成単位が30質量%以上90質量%以下、(b-3)由来の構成単位が5質量%以上50質量%以下の含有量であるビニル系ポリマーであり、より好ましくは(b-1)由来の構成単位が0.5質量%以上20質量%以下、(b-2)由来の構成単位が30質量%以上70質量%以下、(b-3)由来の構成単位が20質量%以上50質量%以下の含有量であるビニル系ポリマーである。
ポリマーBIの酸価は、構成するモノマーの質量比から算出することもできる。また、適当な溶剤にポリマーを溶解又は膨潤させて滴定する方法でも求めることができる。
ポリマーBIIは、有機塩基基を有する。有機塩基基の例は、先に例示したものと同様である。中でも、ポリマーBIIの有機塩基基は、好ましくは第二級アミノ基であり、より好ましくはイミノ基である。
ポリマーBIIとしては、ポリアルキレンイミン、ポリアリルアミン、ポリビニルアミン等が挙げられる。中でも、ポリマーBIIは、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、ポリアルキレンイミンが好ましい。
ポリアルキレンイミンを構成するアルキレンイミンとしては、エチレンイミン、プロピレンイミン、1,2-ブチレンイミン、2,3-ブチレンイミン、1,1-ジメチルエチレンイミン等の炭素数2以上8以下のアルキレンイミンが挙げられるが、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくはエチレンイミンである。前記アルキレンイミンは、1種を単独で又は2種以上を併用して用いてもよい。
ポリアルキレンイミンは、直鎖状又は分岐状であってもよい。ポリアルキレンイミンが分岐状である場合、その構造中に第二級アミノ基(イミノ基)の他、第三級アミノ基、第一級アミノ基を有していてもよい。
上記の重量平均分子量Mwは、ゲル浸透クロマトグラフィー(GPC)により測定することができる。
ポリアルキレンイミンは、公知の方法で合成したものを用いてよく、市販品を用いてもよい。例えば、ポリエチレンイミンの合成法としては、エチレンイミンを二酸化炭素、塩酸、臭化水素酸等を触媒として開環重合させる方法、塩化エチレンとエチレンジアミンを重縮合させる方法、2-オキサゾリドンを加熱する方法等が挙げられる。
ポリアルキレンイミンは、単独で又は2種以上を組み合わせて用いることができる。
PAI/PAO共重合体を構成するPAO鎖は、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、エチレンオキシド、プロピレンオキシド、ブチレンオキシド等の炭素数2以上4以下のアルキレンオキシド由来の単位を含むことが好ましく、エチレンオキシド由来の単位を含むポリエチレンオキシド鎖であることがより好ましい。
PAI/PAO共重合体としては、好ましくは幹としてPAI鎖と枝としてPAO鎖とを有するPAI/PAOグラフト共重合体、網目状のPAI鎖にPAO鎖がアミノ基を介して結合したPAI/PAO共重合体、及びPAI鎖とPAO鎖とを有するPAI/PAOブロック共重合体から選ばれる少なくとも1種である。
PAI/PAOグラフト共重合体の形態としては、幹としてのPAI鎖が直鎖状である形態、幹としてのPAI鎖が分岐状である形態が挙げられる。
PAI/PAOブロック共重合体の重合体ブロックの結合形態としてはジブロック、トリブロック等が挙げられ、PAI/PAOブロック共重合体の具体例としては、PAI/PAOジブロック共重合体、PAI/PAO/PAIトリブロック共重合体等が挙げられる。
PAI/PAO共重合体を構成するPAO鎖の重量平均分子量Mwは、好ましくは300以上、より好ましくは500以上、更に好ましくは1,000以上であり、そして、好ましくは50,000以下、より好ましくは30,000以下、更に好ましくは20,000以下である。
上記の重量平均分子量Mwは、ゲル浸透クロマトグラフィー(GPC)を用いて、PAI/PAO共重合体の製造時に用いる原料のPAI鎖化合物及びPAO鎖化合物の重量平均分子量Mwを測定することにより求めることができる。
PAI/PAOグラフト共重合体において、アルキレンイミン単位の総数に対するグラフトされたPAO鎖を有するアルキレンイミン単位の総数の比(グラフトされたPAO鎖を有するアルキレンイミン単位の総数/アルキレンイミン単位の総数)は、好ましくは0.01以上、より好ましくは0.015以上、更に好ましくは0.02以上であり、そして、好ましくは0.1以下、より好ましくは0.07以下、更に好ましくは0.05以下である。上記の比(グラフトされたPAO鎖を有するアルキレンイミン単位の総数/アルキレンイミン単位の総数)は、1H-NMRにより測定することができる。
PAI/PAO共重合体の市販品としては、Creative PEGWorks社製のPPEシリーズ等が挙げられる。
本発明のインクは、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、カルボン酸Cを含有する。カルボン酸Cの炭素数は、1以上6以下であり、好ましくは1以上3以下である。カルボン酸Cは、1種を単独で又は2種以上を組み合わせて用いることができる。
カルボン酸Cとしては、例えば、飽和又は不飽和の、直鎖又は分岐鎖の脂肪族カルボン酸が挙げられる。カルボン酸Cは、同一分子中にカルボキシ基以外の官能基を有していてもよい。該官能基としては、例えば、アルデヒド基、ハロゲン原子を含む官能基、ヒドロキシ基、チオール基等の少なくとも1種のヘテロ原子を含む官能基等の金属微粒子に対して配位性を有する官能基が挙げられる。中でも、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、カルボン酸Cの同一分子中に、アルデヒド基を有することが好ましい。
カルボン酸Cは、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくはモノカルボン酸を含み、より好ましくはギ酸、酢酸、プロピオン酸、酪酸、イソブタン酸、ヘキサン酸、グリオキシル酸及び乳酸から選ばれる少なくとも1種を含み、更に好ましくはギ酸、酢酸、酪酸、ヘキサン酸及びグリオキシル酸から選ばれる少なくとも1種を含み、より更に好ましくはギ酸、ヘキサン酸及びグリオキシル酸から選ばれる少なくとも1種を含み、更に好ましくはギ酸及びグリオキシル酸から選ばれる少なくとも1種を含み、より更に好ましくはギ酸を含む。
カルボン酸C中のギ酸、酢酸、プロピオン酸、酪酸、イソブタン酸、ヘキサン酸、グリオキシル酸及び乳酸の合計含有量は、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくは80質量%以上、より好ましくは90質量%以上、更に好ましくは95質量%以上、より更に好ましくは98質量%以上、より更に好ましくは実質的に100質量%である。ここで「実質的100質量%」とは、意図せずに含まれる成分を含みうることを意味する。例えば、カルボン酸C中のギ酸、酢酸、プロピオン酸、酪酸、イソブタン酸、ヘキサン酸、グリオキシル酸及び乳酸の合計含有量が実質的に100質量%である場合、意図せずに含まれる成分としては、原料である上記カルボン酸中に含まれる上記ギ酸、酢酸、プロピオン酸、酪酸、イソブタン酸、ヘキサン酸、グリオキシル酸及び乳酸以外のカルボン酸C成分が挙げられる。
カルボン酸C中のギ酸及びグリオキシル酸の合計含有量は、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくは80質量%以上、より好ましくは90質量%以上、更に好ましくは95質量%以上、より更に好ましくは98質量%以上、より更に好ましくは実質的に100質量%である。ここで「実質的100質量%」とは、意図せずに含まれる成分を含みうることを意味する。例えば、カルボン酸C中のギ酸及びグリオキシル酸の合計含有量が実質的に100質量%である場合、意図せずに含まれる成分としては、原料である上記カルボン酸中に含まれる上記ギ酸及びグリオキシル酸以外のカルボン酸C成分が挙げられる。
本発明のインクは、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、アミンDを含有する。アミンDの炭素数は、1以上6以下であり、同様の観点から、好ましくは4以下、さらに好ましくは3以下であり、そして、安全性の観点から、好ましくは2以上である。アミンDは、1種を単独で又は2種以上を組み合わせて用いることができる。
アミンDは、少なくとも1個の、第一級アミノ基、第二級アミノ基、又は第三級アミノ基を含むものである。
中でも、アミンDは、好ましくは第一級アミンを含み、より好ましくはモノアルキルアミンを含み、更に好ましくはn-プロピルアミン、イソプロピルアミン、n-ブチルアミン、tert-ブチルアミン、sec-ブチルアミン及びn-ヘキシルアミンから選ばれる少なくとも1種を含み、更に好ましくはn-プロピルアミン及びn-ヘキシルアミンから選ばれる少なくとも1種を含み、より更に好ましくはn-プロピルアミンを含む。
アミンD中のn-プロピルアミン、イソプロピルアミン、n-ブチルアミン、tert-ブチルアミン、sec-ブチルアミン及びn-ヘキシルアミンの合計含有量は、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくは80質量%以上、より好ましくは90質量%以上、更に好ましくは95質量%以上、より更に好ましくは98質量%以上、より更に好ましくは実質的に100質量%である。ここで「実質的100質量%」とは、意図せずに含まれる成分を含みうることを意味する。例えば、アミンD中のn-プロピルアミン、イソプロピルアミン、n-ブチルアミン、tert-ブチルアミン、sec-ブチルアミン及びn-ヘキシルアミンの合計含有量が実質的に100質量%である場合、意図せずに含まれる成分としては、原料である上記アミン中に含まれる上記n-プロピルアミン、イソプロピルアミン、n-ブチルアミン、tert-ブチルアミン、sec-ブチルアミン及びn-ヘキシルアミン以外のアミンD成分が挙げられる。
アミンD中のn-プロピルアミン及びn-ヘキシルアミンの合計含有量は、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくは80質量%以上、より好ましくは90質量%以上、更に好ましくは95質量%以上、より更に好ましくは98質量%以上、より更に好ましくは実質的に100質量%である。ここで「実質的100質量%」とは、意図せずに含まれる成分を含みうることを意味する。例えば、アミンD中のn-プロピルアミン及びn-ヘキシルアミンの合計含有量が実質的に100質量%である場合、意図せずに含まれる成分としては、原料である上記アミン中に含まれる上記n-プロピルアミン及びn-ヘキシルアミン以外のアミンD成分が挙げられる。
本発明のインクは、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、体積抵抗率を低減する観点、及びインクの取り扱い性を向上させる観点から、好ましくはジオールEを含有する。ジオールEは、1種を単独で又は2種以上を組み合わせて用いることができる。
ジオールEは、1分子中に2つのアルコール性水酸基を有する化合物であれば特に制限はない。ジオールCとしては、エチレングリコール(沸点197℃)、プロピレングリコール(1,2-プロパンジオール)(沸点188℃)、1,2-ブタンジオール(沸点193℃)、1,2-ペンタンジオール(沸点206℃)、1,2-ヘキサンジオール(沸点223℃)等の1,2-アルカンジオール;ジエチレングリコール(沸点245℃)、トリエチレングリコール(沸点287℃)、テトラエチレングリコール(沸点314℃)、ポリエチレングリコール、ジプロピレングリコール(沸点232℃)、トリプロピレングリコール(沸点271℃)等のポリアルキレングリコール;1,3-プロパンジオール(沸点210℃)、1,4-ブタンジオール(沸点230℃)、1,5-ペンタンジオール(沸点242℃)等のα,ω-アルカンジオール;1,3-ブタンジオール(沸点208℃)、3-メチル-1,3-ブタンジオール(沸点203℃)、2-メチル-2,4-ペンタンジオール(沸点196℃)等が挙げられる。
ジオールEは、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくは1,2-アルカンジオール及びポリアルキレングリコールから選ばれる少なくとも1種を含み、より好ましくは1,2-アルカンジオールを含み、更に好ましくはプロピレングリコール及びエチレングリコールから選ばれる少なくとも1種を含み、より更に好ましくはプロピレングリコールを含む。
ジオールE中のプロピレングリコール及びエチレングリコールの合計含有量は、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、体積抵抗率を低減する観点、及びインクの取り扱い性を向上させる観点から、好ましくは80質量%以上、より好ましくは90質量%以上、更に好ましくは95質量%以上、より更に好ましくは98質量%以上、より更に好ましくは実質的に100質量%である。ここで「実質的100質量%」とは、意図せずに含まれる成分を含みうることを意味する。意図せずに含まれる成分としては、例えば、原料である上記ジオール中に含まれる上記プロピレングリコール及びエチレングリコール以外のジオールE成分が挙げられる。
本発明のインクは、本発明の効果を阻害しない範囲で、前記成分以外の他の成分として、ポリマー粒子の分散体等の定着助剤、保湿剤、湿潤剤、浸透剤、界面活性剤、粘度調整剤、消泡剤、防腐剤、防黴剤、防錆剤等の各種添加剤を含有してもよい。
本発明のインクは、公知の方法により予め調製した金属微粒子Aに分散剤としてポリマーB、カルボン酸C、アミンD、及び必要に応じてジオールE、水等を添加及び混合する方法;金属原料化合物、還元剤、及び分散剤としてポリマーBを混合して、該金属原料化合物を還元して金属微粒子の分散体を得た後、カルボン酸C、アミンD、及び必要に応じてジオールE、水等を添加及び混合する方法等により得ることができる。中でも、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、予めポリマーBを含む金属微粒子乾燥粉を得た後、カルボン酸C、アミンD、及び必要に応じてジオール、水等を添加及び混合する方法が好ましい。
金属微粒子乾燥粉は、金属原料化合物、還元剤、及びポリマーBを混合し、該金属原料化合物が還元剤により還元され、ポリマーBで分散されてなる金属微粒子の分散体を得た後、該金属微粒子の分散体を凍結乾燥等により乾燥させて得ることができる。
金属原料化合物としては、前述の金属微粒子Aで例示した金属を含む、無機酸又は有機酸の金属塩、金属酸化物、金属水酸化物、金属硫化物、金属ハロゲン化物等が挙げられる。前記金属塩としては、硝酸塩、亜硝酸塩、硫酸塩、炭酸塩、アンモニウム塩、過塩素酸塩等の無機酸の金属塩;酢酸塩等の有機酸の金属塩などが挙げられる。金属原料化合物は、1種を単独で又は2種以上を混合して用いることができる。中でも、金属原料化合物としては、汎用性及び金属微粒子の生産性の観点から、好ましくは無機酸又は有機酸の金属塩であり、より好ましくは無機酸の金属塩であり、更に好ましくは硝酸の金属塩であり、より更に好ましくは硝酸銀である。
有機還元剤としては、エチレングリコール、プロピレングリコール等のアルコール類;ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド等のアルデヒド類;アスコルビン酸、クエン酸等の酸類及びその塩;エタノールアミン、N-メチルエタノールアミン、N,N-ジメチルエタノールアミン(2-(ジメチルアミノ)エタノール)、N,N-ジエチルエタノールアミン、ジエタノールアミン、N-メチルジエタノールアミン、トリエタノールアミン、プロパノールアミン、N,N-ジメチルプロパノールアミン、ブタノールアミン、ヘキサノールアミン等のアルカノールアミン、n-プロピルアミン、n-ブチルアミン、n-ヘキシルアミン、ジエチルアミン、ジプロピルアミン、ジメチルエチルアミン、ジエチルメチルアミン、トリエチルアミン等のアルキルアミン、エチレンジアミン、トリエチレンジアミン、テトラメチルエチレンジアミン、ジエチレントリアミン、ジプロピレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン等の(ポリ)アルキレンポリアミン等の脂肪族アミン;ピペリジン、ピロリジン、N-メチルピロリジン、モルホリン等の脂環式アミン;アニリン、N-メチルアニリン、トルイジン、アニシジン、フェネチジン等の芳香族アミン;ベンジルアミン、N-メチルベンジルアミン等のアラルキルアミンなどが挙げられる。
無機還元剤としては、水素化ホウ素ナトリウム、水素化ホウ素アンモニウム等の水素化ホウ素塩;水素化アルミニウムリチウム、水素化アルミニウムカリウム等の水素化アルミニウム塩;ヒドラジン、炭酸ヒドラジン等のヒドラジン類;水素ガス等が挙げられる。
還元剤は、1種を単独で又は2種以上を組み合わせて用いてもよい。
金属微粒子の分散体を精製する方法は、特に制限はなく、透析、限外濾過等の膜処理;遠心分離処理等の方法が挙げられる。中でも、不純物を効率的に除去する観点から、膜処理が好ましく、透析がより好ましい。透析に用いる透析膜の材質としては、再生セルロースが好ましい。
透析膜の分画分子量は、不純物を効率的に除去する観点から、好ましくは1,000以上、より好ましくは5,000以上、更に好ましくは10,000以上であり、そして、好ましくは100,000以下、より好ましくは70,000以下である。
本発明のインクは、更に必要に応じて前述の各種添加剤を添加し、フィルター等による濾過処理を行うことにより得ることができる。
本発明のインク中の金属微粒子Aの含有量は、体積抵抗率を低減させて導電性を向上させる観点、及び鏡面性光沢を向上させる観点から、好ましくは10質量%以上、より好ましくは15質量%以上、更に好ましくは20質量%以上、より更に好ましくは25質量%以上であり、そして、保存安定性及びオープンタイム特性を向上させる観点から、好ましくは70質量%以下、より好ましくは60質量%以下、更に好ましくは50質量%以下、より更に好ましくは40質量%以下、より更に好ましくは35質量%以下である。
本発明のインク中のポリマーBの含有量は、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、好ましくは0.5質量%以上、より好ましくは1質量%以上、更に好ましくは1.5質量%以上、より更に好ましくは2質量%以上であり、そして、好ましくは10質量%以下、より好ましくは7質量%以下、更に好ましくは5質量%以下、より更に好ましくは3質量%以下である。
本発明のインク中のカルボン酸Cの含有量は、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、0.7質量%以上であり、好ましくは1質量%以上、より好ましくは1.5質量%以上、更に好ましくは2質量%以上、より更に好ましくは2.5質量%以上、より更に好ましくは3質量%以上、より更に好ましくは4質量%以上であり、そして、15質量%以下であり、好ましくは10質量%以下、より好ましくは7質量%以下である。
本発明のインク中のアミンDの含有量は、金属微粒子の分散安定性を向上させて、インクの保存安定性及びオープンタイム特性を向上させる観点、耐折り曲げ性を向上させる観点、並びに体積抵抗率を低減する観点から、0.7質量%以上であり、好ましくは1質量%以上、より好ましくは1.5質量%以上、更に好ましくは2質量%以上、より更に好ましくは3質量%以上、より更に好ましくは4質量%以上、より更に好ましくは5質量%以上、より更に好ましくは6質量%以上、より更に好ましくは7質量%以上、より更に好ましくは8質量%以上であり、そして、20質量%以下であり、好ましくは17質量%以下、より好ましくは15質量%以下、更に好ましくは13質量%以下、より更に好ましくは11質量%以下である。
前記質量比[ポリマーB/(金属微粒子A+ポリマーB)]は、示差熱熱重量同時測定装置(TG/DTA)を用いて実施例に記載の方法により測定される金属微粒子A及びポリマーBの質量から算出される。
本発明のインク中に含まれる金属微粒子Aの平均粒径は、保存安定性及びオープンタイム特性の観点、及び体積抵抗率を低減させて導電性を向上させる観点、及び鏡面性光沢を向上させる観点から、好ましくは3nm以上、より好ましくは10nm以上、更に好ましくは20nm以上であり、そして、好ましくは100nm以下、より好ましくは70nm以下、更に好ましくは50nm以下、より更に好ましくは40nm以下、より更に好ましくは30nm以下である。金属微粒子Aの平均粒径は、実施例に記載の方法により測定できる。
本発明のインクの30℃における粘度は、保存安定性及びオープンタイム特性の観点から、好ましくは2mPa・s以上、より好ましくは3mPa・s以上、更に好ましくは4mPa・s以上、より更に好ましくは5mPa・s以上であり、そして、好ましくは60mPa・s以下、より好ましくは50mPa・s以下、更に好ましくは30mPa・s以下、より更に好ましくは10mPa・s以下である。前記インクの粘度は、E型粘度計を用いて実施例に記載の方法により測定される。
本発明のインクの20℃のpHは、保存安定性及びオープンタイム特性の観点から、好ましくは7.0以上、より好ましくは7.2以上、更に好ましくは7.5以上である。また、部材耐性、皮膚刺激性の観点から、pHは、好ましくは11以下、より好ましくは10以下、更に好ましくは9.5以下である。前記インクのpHは、常法により測定できる。
本発明の印刷物の製造方法は、前記金属微粒子含有インクを用いて基材に印刷し、該基材に金属膜が形成された印刷物を得る方法が好ましい。
これにより、導電性、鏡面性光沢等に優れた金属膜が形成された印刷物を得ることができる。前記金属微粒子含有インクを用いる印刷において、パターン化された印刷画像を基材に形成することによりパターン化された金属膜を形成することができ、このパターン化された金属膜は導電回路として用いることができる。すなわち、本発明の印刷物の製造方法は、基材に導電回路が形成された印刷物の製造方法として用いることが好ましい。
なお、導電回路が形成された印刷物の製造においては、前記基材は「基板」と呼ぶことがある。
前記基材としては、例えば、紙;布帛;樹脂;金属;ガラス;セラミック又はこれらの複合材料などが挙げられる。
紙基材としては、塗工紙(コート紙、アート紙等)、非塗工紙、普通紙、クラフト紙、合成紙、加工紙、板紙等が挙げられる。
基材に用いる布帛としては、綿、絹、麻等の天然繊維、レーヨン繊維、アセテート繊維、ナイロン繊維、ポリエステル繊維等の合成繊維からなる布帛、又はこれら繊維の2種以上からなる混紡布帛などが挙げられる。
樹脂製基材としては、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリブチレンテレフタレート(PBT)、ポリプロピレン(PP)、ポリアミド(PA)、ポリイミド(PI)、ポリ塩化ビニル(PVC)、ポリメチルメタクリレート(PMMA)、ポリスチレン(PS)、アクリロニトリル-ブタジエン-スチレン共重合体(ABS)、アクリロニトリル-スチレン共重合体(AS)、ポリカーボネート(PC)等の合成樹脂フィルムが挙げられる。
金属製基材としては、金、銀、銅、パラジウム、プラチナ、アルミニウム、ニッケル、スズ等の金属を用いた基板などが挙げられる。
これらの中でも、前記基材は、耐折り曲げ性の観点から、好ましくは紙基材及び樹脂製基材から選ばれる少なくとも1種であり、より好ましくは紙基材である。
また、前記基材は、リジット基材であってもよく、フレキシブル基材でもあってもよいが、前記金属微粒子含有インクは耐折り曲げ性に優れる金属膜を形成できる観点から、フレキシブル基材であることが好ましい。
前記金属微粒子含有インクの基材への付与量は、形成する回路又は電極の大きさや種類、所望とする鏡面性光沢の程度や意匠に応じて適宜調整することができる。
本発明の金属微粒子含有インクをインクジェット印刷用として用いる場合には、該インクを公知のインクジェット印刷装置に装填し、インク液滴として基材に吐出して印刷画像を形成することができる。
インクジェット印刷装置としてはサーマル式及びピエゾ式があるが、前記インクはサーマル式のインクジェット印刷用として用いることがより好ましい。
インクジェットヘッドのヘッド電圧は、印刷の効率性等の観点から、好ましくは5V以上、より好ましくは10V以上、更に好ましくは15V以上であり、そして、好ましくは40V以下、より好ましくは35V以下、更に好ましくは30V以下である。
ヘッドの駆動周波数は、印刷の効率性等の観点から、好ましくは1kHz以上、より好ましくは5kHz以上、更に好ましくは10kHz以上であり、そして、好ましくは50kHz以下、より好ましくは40kHz以下、更に好ましくは35kHz以下である。
本発明に係るインクの基材への付与量は、固形分として、好ましくは0.5g/m2以上、より好ましくは1g/m2以上、更に好ましくは2g/m2以上であり、そして、好ましくは20g/m2以下、より好ましくは15g/m2以下、更に好ましくは10g/m2以下である。
本発明において、印刷の解像度は、好ましくは200dpi以上、より好ましくは300dpi以上であり、そして、好ましくは1,000dpi以下、より好ましくは800dpi以下、更に好ましくは600dpi以下である。ここで、本明細書における「解像度」とは、基材に形成される1インチ(2.54cm)あたりのドットの数をいう。例えば「解像度が600dpi」とは、ノズル列の長さあたりのノズル孔の個数が600dpi(ドット/インチ)配置されたラインヘッドを用いて、基材にインク液滴を吐出すると、それに対応する1インチあたり600dpiのドットの列が、基材の搬送方向と垂直な方向に形成され、そして、基材を搬送方向に移動させながらインク液滴を吐出すると、基材には搬送方向にも1インチあたり600dpiのドットの列が形成されることをいう。本明細書では、基材の搬送方向に対して垂直な方向の解像度と、搬送方向の解像度は同じ値として表される。
本発明の印刷物の製造方法は、体積抵抗率を低減させて導電性を向上させる観点、及び鏡面性光沢を向上させる観点、並びに耐折り曲げ性を向上させる観点から、前記インクを用いて基材に印刷した後、該基材上のインク被膜中の金属微粒子Aを焼結させる焼結処理を行うことが好ましい。
焼結処理により、インク被膜中のインク溶媒を蒸発乾燥させて、更に金属微粒子Aを焼結させて体積抵抗率の低い金属膜からなる導電回路を形成することができる。
焼結処理の周辺環境の相対湿度は、好ましくは20%以上、より好ましくは30%以上、更に好ましくは40%以上であり、そして、好ましくは65%以下、より好ましくは60%以下である。
中でも、焼結処理は、100℃以上の高温で処理した後、低温で保管して処理することが好ましい。ここで、低温処理は、好ましくは室温(10℃以上35℃以下)で保管して処理を行うことが好ましい。
焼結処理における高温処理の時間は、処理の温度によって適宜調整することができるが、金属膜の抵抗率を低減する観点から、好ましくは1分間以上、より好ましくは5分間以上、更に好ましくは7分間以上であり、そして、生産性の観点から、好ましくは6時間以下、より好ましくは3時間以下、更に好ましくは1時間以下、より更に好ましくは30分間以下である。
焼結処理における低温処理の時間は、処理の温度によって適宜調整することができるが、金属膜の抵抗率を低減する観点から、好ましくは1時間以上、より好ましくは3時間以上、更に好ましくは6時間以上、より更に好ましくは12時間以上であり、そして、生産性の観点から、好ましくは36時間以下、より好ましくは24時間以下である。
焼結処理は、空気雰囲気下であってもよく、窒素ガス等の不活性ガス雰囲気下であってもよいが、前記基材が酸化されやすい金属である場合には、窒素ガス雰囲気下であることが好ましい。
焼結処理の方法は、特に制限はなく、基材のインク被膜が形成された表面と反対側の面にヒーターを接触させて加熱する方法;基材上のインク被膜面に熱風を付与して加熱する方法;基材上のインク被膜面にヒーターを近づけて加熱する方法;インク被膜を形成した基材を、温度を一定に保つことができる恒温装置内で保管する方法;常圧又は高圧で高温蒸気を用いる蒸気養生によって加熱する方法:近赤外光、紫外光等の光照射により加熱する方法等が挙げられる。
<1>
ポリマーBで分散されてなる金属微粒子A、カルボン酸C、及びアミンDを含有する金属微粒子含有インクであって、
ポリマーBが、有機酸基及び有機塩基基から選ばれる少なくとも1種を有し、
カルボン酸Cの炭素数が、1以上6以下であり、
アミンDの炭素数が、1以上6以下であり、
カルボン酸Cの含有量が、0.7質量%以上15質量%以下であり、
アミンDの含有量が、0.7質量%以上20質量%以下である、金属微粒子含有インク。
<2>
ポリマーBで分散されてなる金属微粒子A、カルボン酸C、及びアミンDを含有する金属微粒子含有インクであって、
ポリマーBが、有機酸基及び有機塩基基から選ばれる少なくとも1種を有し、
カルボン酸Cの炭素数が、1以上6以下であり、
アミンDの炭素数が、1以上6以下であり、
カルボン酸Cの含有量が、0.7質量%以上15質量%以下であり、
アミンDの含有量が、0.7質量%以上20質量%以下であり、
ポリマーBがカルボキシ基及びイミノ基から選ばれる少なくとも1種を含み、
カルボン酸Cがモノカルボン酸を含み、
アミンDが第一級アミンを含み、
金属微粒子Aを構成する金属が銀、銅及びニッケルから選ばれる少なくとも1種を含む、<1>に記載の金属微粒子含有インク。
<3>
ポリマーBで分散されてなる金属微粒子A、カルボン酸C、及びアミンDを含有する金属微粒子含有インクであって、
ポリマーBが、有機酸基及び有機塩基基から選ばれる少なくとも1種を有し、
カルボン酸Cの炭素数が、1以上6以下であり、
アミンDの炭素数が、1以上6以下であり、
カルボン酸Cの含有量が、0.7質量%以上15質量%以下であり、
アミンDの含有量が、0.7質量%以上20質量%以下であり、
ポリマーBが、モノマー(b-1)として(メタ)アクリル酸及びマレイン酸から選ばれる少なくとも1種由来の構成単位と、モノマー(b-2)としてスチレン及びスチレン誘導体から選ばれる少なくとも1種由来の構成単位とを含むビニル系ポリマー及びポリエチレンイミンから選ばれる少なくとも1種を含み、
カルボン酸Cがギ酸、酢酸、プロピオン酸、酪酸、イソブタン酸、ヘキサン酸、グリオキシル酸及び乳酸から選ばれる少なくとも1種を含み、
アミンDがモノアルキルアミンを含み、
金属微粒子Aを構成する金属が銀、銅及びニッケルから選ばれる少なくとも1種を含む、<1>又は<2>に記載の金属微粒子含有インク。
<4>
ポリマーBで分散されてなる金属微粒子A、カルボン酸C、及びアミンDを含有する金属微粒子含有インクであって、
ポリマーBが、有機酸基及び有機塩基基から選ばれる少なくとも1種を有し、
カルボン酸Cの炭素数が、1以上6以下であり、
アミンDの炭素数が、1以上6以下であり、
カルボン酸Cの含有量が、0.7質量%以上15質量%以下であり、
アミンDの含有量が、0.7質量%以上20質量%以下であり、
ポリマーBが、モノマー(b-1)として(メタ)アクリル酸及びマレイン酸から選ばれる少なくとも1種由来の構成単位と、モノマー(b-2)としてスチレン及びスチレン誘導体から選ばれる少なくとも1種由来の構成単位と、モノマー(b-3)としてアルコキシポリエチレングリコール(メタ)アクリレート由来の構成単位とを含むビニル系ポリマーを含み、
カルボン酸Cがギ酸、酢酸、酪酸、ヘキサン酸及びグリオキシル酸から選ばれる少なくとも1種を含み、
アミンDがn-プロピルアミン、イソプロピルアミン、n-ブチルアミン、tert-ブチルアミン、sec-ブチルアミン及びn-ヘキシルアミンから選ばれる少なくとも1種を含み、
金属微粒子Aを構成する金属が銀,銅及びニッケルから選ばれる少なくとも1種を含む、<1>~<3>のいずれか1つに記載の金属微粒子含有インク。
<5>
ポリマーBで分散されてなる金属微粒子A、カルボン酸C、及びアミンDを含有する金属微粒子含有インクであって、
ポリマーBが、有機酸基及び有機塩基基から選ばれる少なくとも1種を有し、
カルボン酸Cの炭素数が、1以上6以下であり、
アミンDの炭素数が、1以上6以下であり、
カルボン酸Cの含有量が、0.7質量%以上15質量%以下であり、
アミンDの含有量が、0.7質量%以上20質量%以下であり、
ポリマーBが、モノマー(b-1)として(メタ)アクリル酸及びマレイン酸から選ばれる少なくとも1種由来の構成単位が0.5質量%以上20質量%以下、モノマー(b-2)としてスチレン及びスチレン誘導体から選ばれる少なくとも1種由来の構成単位が30質量%以上90質量%以下、モノマー(b-3)としてアルコキシポリエチレングリコール(メタ)アクリレート由来の構成単位が5質量%以上50質量%以下の含有量であるビニル系ポリマーを含み、
カルボン酸Cがギ酸、ヘキサン酸及びグリオキシル酸から選ばれる少なくとも1種を含み、
アミンDがn-プロピルアミン及びn-ヘキシルアミンから選ばれる少なくとも1種を含み、
金属微粒子Aを構成する金属が銀,銅及びニッケルから選ばれる少なくとも1種を含む、<1>~<4>のいずれか1つに記載の金属微粒子含有インク。
<6>
ポリマーBで分散されてなる金属微粒子A、カルボン酸C、及びアミンDを含有する金属微粒子含有インクであって、
ポリマーBが、有機酸基及び有機塩基基から選ばれる少なくとも1種を有し、
カルボン酸Cの炭素数が、1以上6以下であり、
アミンDの炭素数が、1以上6以下であり、
カルボン酸Cの含有量が、0.7質量%以上15質量%以下であり、
アミンDの含有量が、0.7質量%以上20質量%以下であり、
ポリマーBが、モノマー(b-1)として(メタ)アクリル酸及びマレイン酸から選ばれる少なくとも1種由来の構成単位が0.5質量%以上20質量%以下、モノマー(b-2)としてスチレン及びスチレン誘導体から選ばれる少なくとも1種由来の構成単位が30質量%以上70質量%以下、モノマー(b-3)としてアルコキシポリエチレングリコール(メタ)アクリレート由来の構成単位が20質量%以上50質量%以下の含有量であるビニル系ポリマーを含み、
カルボン酸Cがギ酸及びグリオキシル酸から選ばれる少なくとも1種を含み、
アミンDがn-プロピルアミンを含み、
金属微粒子Aを構成する金属が銀を含む、<1>~<5>のいずれか1つに記載の金属微粒子含有インク。
<7>
金属微粒子含有インク中のカルボン酸Cの含有量に対するアミンDの含有量の質量比[アミンD/カルボン酸C]が、0.5以上6以下である、<1>~<6>のいずれか1つに記載の金属微粒子含有インク。
<8>
金属微粒子含有インク中の金属微粒子Aの含有量が10質量%以上70質量%以下であり、ポリマーBの含有量が0.5質量%以上10質量%以下である、<1>~<7>のいずれか1つに記載の金属微粒子含有インク。
<9>
金属微粒子含有インクがジオールEを含有する、<1>~<8>のいずれか1つに記載の金属微粒子含有インク。
<10>
金属微粒子含有インク中のジオールEの含有量が5質量%以上60質量%以下である、<9>に記載の金属微粒子含有インク。
<11>
30℃における粘度が、2mPa・s以上50mPa・s以下である、<1>~<10>のいずれか1つに記載の金属微粒子含有インク。
<12>
インクジェット印刷用である、<1>~<11>のいずれか1つに記載の金属微粒子含有インク。
<13>
<1>~<12>のいずれか1つに記載の金属微粒子含有インクを用いて基材に印刷し、該基材に導電回路が形成された印刷物を得る、印刷物の製造方法。
各種物性は、以下の方法により測定又は算出した。
N,N-ジメチルホルムアミドに、リン酸及びリチウムブロマイドをそれぞれ60mmol/Lと50mmol/Lの濃度となるように溶解した液を溶離液として、ゲル浸透クロマトグラフィー法〔東ソー株式会社製GPC装置(HLC-8320GPC)、東ソー株式会社製カラム(TSKgel SuperAWM-H、TSKgel SuperAW3000、TSKgel guardcolumn Super AW-H)、流速:0.5mL/min〕により、標準物質として分子量既知の単分散ポリスチレンキット〔PStQuick B(F-550、F-80、F-10、F-1、A-1000)、PStQuick C(F-288、F-40、F-4、A-5000、A-500)、東ソー株式会社製〕を用いて測定した。
測定サンプルは、ガラスバイアル中にポリマーBI 0.1gを前記溶離液10mLと混合し、25℃で10時間、マグネチックスターラーで撹拌し、シリンジフィルター(DISMIC-13HP PTFE 0.2μm、アドバンテック東洋株式会社製)で濾過したものを用いた。
示差熱熱重量同時測定装置(TG/DTA)「STA7200RV」(株式会社日立ハイテクサイエンス社製)を用いて、試料10mgをアルミパンセルに計量し、10℃/分の昇温速度で35℃から550℃まで昇温し、50mL/分の窒素フロー下で質量減少を測定した。200℃から550℃までの質量減少をポリマーBの質量、550℃での残質量を金属微粒子Aの質量として、質量比[ポリマーB/(金属微粒子A+ポリマーB)]を算出した。
レーザー粒子解析システム「ELS-8000」(大塚電子株式会社製)を用いて、動的光散乱法により粒径を測定し、キュムラント法解析により算出した。測定条件は、温度25℃、入射光と検出器との角度90°、積算回数100回であり、分散溶媒の屈折率として水の屈折率(1.333)を入力した。測定サンプルには、試料をスクリュー管(マルエム株式会社製No.5)に計量し、固形分濃度が5×10-3質量%になるように水を加えてマグネチックスターラーを用いて25℃で1時間撹拌したものを用いた。
E型粘度計(東機産業株式会社製、型番:TV-25、標準コーンロータ1°34’×R24使用、回転数100rpm)を用いて、30℃におけるインクの粘度を測定した。
温度計、100mL窒素バイパス付き滴下ロート2本、還流装置を具備した1000mL四つ口丸底フラスコに、1,4-ジオキサン100gを入れ、オイルバスにて該フラスコの内温を80℃まで加温した後、窒素バブリングを10分間行った。次いで、ポリマーBIの原料モノマーとして、98%アクリル酸(富士フイルム和光純薬株式会社製、特級試薬)3g、メトキシポリエチレングリコール(EO9モル)アクリレート(新中村化学工業株式会社製「NKエステルAM-90G」)37g、及びスチレン(富士フイルム和光純薬株式会社製、特級試薬)60gと、3-メルカプトプロピオン酸(富士フイルム和光純薬株式会社製、特級試薬)1.5gとをポリビーカー中で溶解し、滴下ロート(1)に入れた。別途、1,4-ジオキサン20g及び2,2’-アゾビス(2,4-ジメチルバレロニトリル)(富士フイルム和光純薬株式会社製「V-65」、重合開始剤)0.2gをポリビーカー中で溶解し、滴下ロート(2)に入れた。次いで、上記フラスコにむけ、滴下ロート(1)及び滴下ロート(2)内の混合物を同時にそれぞれ90分かけて滴下した。その後、該フラスコ内の内温を90℃に昇温した後、更に1時間撹拌を続けた。その後、室温まで冷却し、回転式蒸留装置「ロータリーエバポレーターN-1000S」(東京理化器械株式会社製)を用いて、回転数50rpm、温浴を80℃に調整し、圧力100トールで留去物がなくなるまで蒸留を行った。その後、減圧乾燥機「VO420」(アドバンテック東洋株式会社製)を用い、温度110℃、圧力50トールで48時間乾燥させることで、ポリマーBI-1(アクリル酸/メトキシポリエチレングリコール(EO9モル)アクリレート/スチレン共重合体、酸価:23mgKOH/g、Mn:8,200)を得た。
調製例1において、ポリマーBIの原料モノマーを、98%アクリル酸100gのみに変更した以外は同様にして、ポリマーBI-2(ポリアクリル酸、酸価:780mgKOH/g、Mn:7,700)を得た。
調製例1において、ポリマーBIの原料モノマーを、98%アクリル酸3g、メトキシポリエチレングリコール(EO9モル)アクリレート17g、及びスチレン80gに変更した以外は同様にして、ポリマーBI-3(アクリル酸/メトキシポリエチレングリコール(EO9モル)アクリレート/スチレン共重合体、酸価:23mgKOH/g、Mn:7,500)を得た。
調製例1において、ポリマーBIの原料モノマーを、98%アクリル酸3g及びスチレン97gに変更した以外は同様にして、ポリマーBI-4(アクリル酸/スチレン共重合体、酸価:23mgKOH/g、Mn:5,900)を得た。
ポリマーBIIとしてポリエチレンイミン(富士フイルム和光純薬株式会社製、試薬、重量平均分子量約10,000)を、減圧乾燥機「VO420」(アドバンテック東洋株式会社製)を用い、温度110℃、圧力50トールで48時間乾燥させることで、ポリマーBII-1を得た。
〔金属微粒子乾燥粉の製造〕
(工程1)
1000mLのガラスビーカー中に、還元剤としてN,N-ジメチルエタノールアミン(以下、「DMAE」ともいう)を23g入れ、マグネチックスターラーで撹拌しながらオイルバスで40℃に加温した。別途100mLのビーカーに、金属原料化合物として硝酸銀を140g、分散剤としてポリマーBI-1を8g、イオン交換水を70g投入し、40℃で、マグネチックスターラーを用いて目視で透明になるまで撹拌し、混合液を得た。
次いで、得られた混合液を1000mLの滴下ロートに入れ、該混合液を40℃に保持したDMAEに30分かけて滴下した。その後、オイルバスで反応液の温度を40℃に制御しながら5時間撹拌し、次いで空冷して、分散された銀微粒子を含有する濃茶色の分散体を得た。
工程1で得られた分散体全量を、透析チューブ(REPLIGEN社製「スペクトラ/ポア6」、透析膜:再生セルロース、分画分子量(MWCO)=50K)に投入し、チューブ上下をクローサーにて密封した。このチューブを、5Lガラスビーカー中の5Lのイオン交換水に浸漬し、水温を20~25℃に保持して1時間撹拌した。その後、イオン交換水を1時間ごとに全量交換する作業を3回繰り返した後、1時間おきにサンプリングを行い、上記(2)の示差熱熱重量同時測定装置(TG/DTA)を用いた方法により測定される分散剤B及び金属微粒子Aの質量から算出した質量比[ポリマーB/金属微粒子A]が2.5/30(質量比[ポリマーB/(金属微粒子A+ポリマーB)]=2.5/32.5)になった時点で透析を終了し、精製した分散体を得た。
工程2で得られた精製した分散体を、ドライチャンバー(東京理化器械株式会社製、型式:DRC-1000)を付属した凍結乾燥機(東京理化器械株式会社製、型式:FDU-2110)を用いて、乾燥条件(-25℃1時間凍結、-10℃9時間減圧、25℃5時間減圧。減圧度5Pa)で凍結乾燥することにより、金属微粒子乾燥粉1を得た。
500mLのポリエチレン製ビーカーに、金属微粒子乾燥粉1を32.5g、カルボン酸Cとしてギ酸(富士フイルム和光純薬株式会社製、特級)5g、アミンDとしてn-プロピルアミン(富士フイルム和光純薬株式会社製、特級)10g、ジオールEとしてプロピレングリコール30g、イオン交換水22.3g、及びアセチレングリコール系界面活性剤(日信化学工業株式会社製「サーフィノール104PG-50」2,4,7,9-テトラメチル-5-デシン-4,7-ジオールのプロピレングリコール溶液、有効分50%)0.2gを投入し、マグネチックスターラーで撹拌しながら超音波分散機(株式会社日本精機製作所製、型式:US-3001)で3時間分散した。その後、5μmのディスポーザルメンブレンフィルター(ザルトリウス社製、ミニザルト)を用いて濾過を行い、金属微粒子含有インクを得た。得られたインクを下記の方法の評価に供した。
温度25±1℃、相対湿度30±5%の環境で、インクジェットプリンター(ヒューレット・パッカード株式会社製、型番:デスクジェット6122、サーマル方式)の黒カートリッジ内のインクを前記金属微粒子含有インクに詰め替えた。次いで、プリンターのユーティリティからクリーニング操作を1回行った。ブラックヘッドの全ノズルで問題なく吐出可能となった状態から、同インクジェットプリンターを用いて、基材として市販のペーパー基板「PowerCoat XD 200」(Arjowggings社製、厚み200μm)に横204mm×縦275mmの大きさにフォトショップ(登録商標)上でRGBを0として作成したベタ画像を印刷した〔印刷条件=用紙種類:写真光沢紙、モード設定:きれい、グレースケール〕。
次いで、インク被膜を形成したペーパー基板を150℃のホットステージ上で60分加熱した後、温度25℃、相対湿度55%の環境で24時間保管して、焼結処理を行い、ペーパー基板上に金属膜が形成された印刷物を得た。得られた印刷物を下記の方法で評価に供した。
実施例1のインクの製造において、カルボン酸C又はアミンDの種類、又はインクの組成を表1に従って変更した以外は同様にして、金属微粒子含有インク及び印刷物を得た。
実施例1の金属微粒子乾燥粉の製造において、分散剤の種類を表1に示すように変更した以外は同様にして金属微粒子乾燥粉2~5,51をそれぞれ得た。次いで、実施例1において金属微粒子乾燥粉1に代えて金属微粒子乾燥粉2~5,51をそれぞれ用い、金属微粒子含有インク及び印刷物を得た。なお、比較例1においては分散剤としてポリマーBI-1に代えてチオリンゴ酸(富士フイルム和光純薬株式会社製、特級試薬)を用いた。
実施例1の金属微粒子乾燥粉の製造における工程1で、1000mLのガラスビーカー中に、金属原料化合物として硫酸銅(富士フイルム和光純薬株式会社製、特級)を140g、分散剤としてポリマーB1-1を8g、イオン交換水を70g投入し、40℃で、マグネチックスターラーを用いて目視で透明になるまで撹拌した。マグネチックスターラーで撹拌しながらオイルバスで40℃に加温した。
次いで、100mLの滴下ロートに、還元剤としてヒドラジン1水和物(富士フイルム和光純薬株式会社製、特級)25gをいれ、上記ガラスビーカー中に3時間かけて滴下した。その後、オイルバスで反応液の温度を40℃に制御しながら5時間撹拌し、次いで空冷して、分散された銅微粒子を含有する分散体を得た。
その後は、実施例1の工程2及び工程3と同様にして金属微粒子乾燥粉6を得た。次いで、実施例1において金属微粒子乾燥粉1に代えて金属微粒子乾燥粉6を用い、金属微粒子含有インク及び印刷物を得た。
実施例19の金属微粒子乾燥粉の製造における工程1で、金属原料化合物として硫酸銅を無水塩化ニッケル(富士フイルム和光純薬株式会社製、試薬)に変更した以外は同様にして金属微粒子乾燥粉7を得た。次いで、実施例1において金属微粒子乾燥粉1に代えて金属微粒子乾燥粉7を用い、金属微粒子含有インク及び印刷物を得た。
〔保存安定性の評価〕
実施例及び比較例で得られたインク20gを、上記のインクジェット印刷で用いたインクジェットプリンターの黒カートリッジに詰め替えて密封し、40℃の恒温槽で14日間保存した。次いで、常温(25℃)にて1日静置した後、前述の測定方法と同様の方法で保存後のインクの粘度を測定した。下記式より保存前後の粘度維持率を算出し、インクの保存安定性の指標とした。結果を表2に示す。粘度維持率が100%に近いほど、保存安定性に優れる。
粘度維持率(%)=〔保存後の粘度(mPa・s)/保存前の粘度(mPa・s)〕×100
実施例及び比較例で得られた印刷物を断面試料作製装置「IB-19520CCP」(日本電子株式会社製)を用いて加工し、平滑な切断面を作成した試験片を得た。
次いで、試験片をSEM試料台(日新EM株式会社、Type-T)にSEM用アルミ基材カーボン両面テープ(日新EM株式会社、カタログ番号732)で張り付け、電界放出形走査電子顕微鏡「FE-SEM」(株式会社日立ハイテク製、型式:S-4800)を用いて、SEMモード、加速電圧10kVの条件で切断面を観察し、二次電子像を得た。該二次電子像中の金属膜の10点で金属膜の厚みを測定し、算術平均により金属膜の厚みtを得た。
次いで、同試験片を、抵抗率計(本体:ロレスタ-GP、四探針プローブ:PSPプローブ、いずれも株式会社三菱ケミカルアナリテック社製)を用いて測定し、上記で測定した金属膜の厚みtを前記抵抗率計に入力することにより体積抵抗率を表示させた。上記試験片の他の場所でも同様に測定し、合計10か所の算術平均により、体積抵抗率ρvを得た。結果を表2に示す。
実施例及び比較例で得られた印刷物を、折り曲げ試験機「Elcometer 1500 円筒マンドレルセット、スタンド」(エルコメーター社製)にセットし、JIS K5600-5-1に準拠して、交換用円筒マンドレルを直径32mmから小さいものに順に交換して耐折り曲げ性試験を行った。クラックが発生しなかった円筒マンドレルの最小直径(mm)を耐折り曲げ性の指標として用いた。結果を表2に示す。クラックが発生しなかった円筒マンドレルの最小直径が小さいほど耐折り曲げ性に優れる。
上記インクジェット印刷において、クリーニング操作を1回行った後、ノズル面を保護することなく5分間そのまま静置した。その後、上記と同様の印刷条件でインクジェット印刷を開始し、ノズル欠けの有無を確認した。ノズル欠けが見られない場合には、更にクリーニング操作を1回行った後、ノズル面を保護することなく10分間そのまま放置し、上記と同様の印刷条件でインクジェット印刷を開始し、ノズル欠けの有無を確認した。同様に5分ずつ放置時間を増やし、最長180分まで行った。ノズル欠けが見られなかった最長の時間をオープンタイム(分)とした。なお、「オープンタイム180分」とは、放置時間が180分でもノズル欠けが見られなかったことを示す。結果を表2に示す。
Claims (14)
- ポリマーBで分散されてなる金属微粒子A、カルボン酸C、及びアミンDを含有する金属微粒子含有インクであって、
ポリマーBが、有機酸基及び有機塩基基から選ばれる少なくとも1種を有し、
カルボン酸Cの炭素数が、1以上6以下であり、
アミンDの炭素数が、1以上6以下であり、
カルボン酸Cの含有量が、0.7質量%以上15質量%以下であり、
アミンDの含有量が、0.7質量%以上20質量%以下である、金属微粒子含有インク。 - 金属微粒子含有インク中のカルボン酸Cの含有量に対するアミンDの含有量の質量比[アミンD/カルボン酸C]が、0.5以上6以下である、請求項1に記載の金属微粒子含有インク。
- ポリマーBがカルボキシ基及びイミノ基から選ばれる少なくとも1種を含む、請求項1又は2に記載の金属微粒子含有インク。
- カルボン酸Cがモノカルボン酸を含む、請求項1~3のいずれかに記載の金属微粒子含有インク。
- アミンDがモノアルキルアミンを含む、請求項1~4のいずれかに記載の金属微粒子含有インク。
- 金属微粒子Aを構成する金属が銀、銅及びニッケルから選ばれる少なくとも1種を含む、請求項1~5のいずれかに記載の金属微粒子含有インク。
- 金属微粒子含有インク中の金属微粒子Aの含有量が10質量%以上70質量%以下である、請求項1~6のいずれかに記載の金属微粒子含有インク。
- 金属微粒子含有インク中のポリマーBの含有量が0.5質量%以上10質量%以下である、請求項1~7のいずれかに記載の金属微粒子含有インク。
- ポリマーBが、カルボキシ基を有するモノマー(b-1)由来の構成単位と疎水性モノマー(b-2)由来の構成単位とを含むビニル系ポリマーである、請求項1~8のいずれかに記載の金属微粒子含有インク。
- 金属微粒子含有インクがジオールEを含有する、請求項1~9のいずれかに記載の金属微粒子含有インク。
- 金属微粒子含有インク中のジオールEの含有量が5質量%以上60質量%以下である、請求項10に記載の金属微粒子含有インク。
- 30℃における粘度が、2mPa・s以上50mPa・s以下である、請求項1~11のいずれかに記載の金属微粒子含有インク。
- インクジェット印刷用である、請求項1~12のいずれかに記載の金属微粒子含有インク。
- 請求項1~13のいずれかに記載の金属微粒子含有インクを用いて基材に印刷し、該基材に導電回路が形成された印刷物を得る、印刷物の製造方法。
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CN202180087244.6A CN116724092A (zh) | 2020-12-28 | 2021-06-29 | 含有金属微粒的油墨 |
US18/259,523 US20240059918A1 (en) | 2020-12-28 | 2021-06-29 | Metallic fine particle-containing ink |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009074171A (ja) | 2007-08-30 | 2009-04-09 | Mitsuboshi Belting Ltd | 金属コロイド粒子およびその分散液 |
JP2009227736A (ja) * | 2008-03-19 | 2009-10-08 | Mitsuboshi Belting Ltd | インクジェット印刷用インキ組成物 |
JP2012207049A (ja) * | 2011-03-11 | 2012-10-25 | Bando Chemical Industries Ltd | コロイド分散液 |
JP2013508934A (ja) * | 2009-10-26 | 2013-03-07 | ハンワ ケミカル コーポレイション | カルボン酸を用いた伝導性金属薄膜の製造方法 |
JP2014210847A (ja) * | 2013-04-17 | 2014-11-13 | 東ソー株式会社 | 導電性銅インク組成物 |
WO2021132446A1 (ja) * | 2019-12-27 | 2021-07-01 | 花王株式会社 | 金属微粒子含有インク |
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- 2021-06-29 EP EP21914939.0A patent/EP4269509A1/en active Pending
- 2021-06-29 WO PCT/JP2021/024501 patent/WO2022145077A1/ja active Application Filing
- 2021-06-29 US US18/259,523 patent/US20240059918A1/en active Pending
- 2021-06-29 CN CN202180087244.6A patent/CN116724092A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009074171A (ja) | 2007-08-30 | 2009-04-09 | Mitsuboshi Belting Ltd | 金属コロイド粒子およびその分散液 |
JP2009227736A (ja) * | 2008-03-19 | 2009-10-08 | Mitsuboshi Belting Ltd | インクジェット印刷用インキ組成物 |
JP2013508934A (ja) * | 2009-10-26 | 2013-03-07 | ハンワ ケミカル コーポレイション | カルボン酸を用いた伝導性金属薄膜の製造方法 |
JP2012207049A (ja) * | 2011-03-11 | 2012-10-25 | Bando Chemical Industries Ltd | コロイド分散液 |
JP2014210847A (ja) * | 2013-04-17 | 2014-11-13 | 東ソー株式会社 | 導電性銅インク組成物 |
WO2021132446A1 (ja) * | 2019-12-27 | 2021-07-01 | 花王株式会社 | 金属微粒子含有インク |
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US20240059918A1 (en) | 2024-02-22 |
JP2022104504A (ja) | 2022-07-08 |
JP7129117B2 (ja) | 2022-09-01 |
CN116724092A (zh) | 2023-09-08 |
EP4269509A1 (en) | 2023-11-01 |
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