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
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/108—Hydrocarbon resins

Definitions

• the present invention relates to a water-based ink containing fine metal particles and a method for producing a printed matter.
• Metal fine particles are expected to develop a wide variety of industrial applications due to the diversity of functions and physical properties that are manifested by using metals that have been miniaturized to nano-size. For example, it is known that a design with metallic luster can be obtained by using fine metal particles for printing. are being studied to improve the performance of
• Patent Document 1 provides an ink composition excellent in dispersion stability that is optimal for forming a glossy coating having sufficient scratch resistance and weather resistance.
• an ink composition comprising a metal colloid containing metal particles and a nonionic resin emulsion, wherein the content of the resin emulsion with respect to the metal particles is 2.5 to 125% by mass. is disclosed.
• Patent Document 2 provides an ink composition which is excellent in ejection stability and can easily form an image excellent in gas resistance.
• An ink composition characterized by having an equilibrium moisture content of 2% by mass or more and 7.8% by mass or less when the composition composed of the components is left in an ambient temperature of 23° C. and a humidity of 50% RH. is disclosed.
• Patent Document 3 provides an ink composition that can exhibit sufficient luster even on cloudy or rainy days and weak light such as indoor lights, and even if it is stored for a long time.
• a glittering ink composition containing at least a hologram pigment having an average particle size of 250 to 700 ⁇ m and a liquid medium is disclosed for the purpose of providing a glittering ink composition containing a hologram pigment that does not form a hard cake. ing.
• the present invention relates to a water-based ink containing fine metal particles containing fine metal particles A dispersed with polymer B, polyolefin wax particles C, amine D, and water.
• the present invention relates to a water-based ink containing fine metal particles having excellent document offset resistance and a method for producing a printed matter using the water-based ink containing fine metal particles.
• a water-based ink containing fine metal particles which contains fine metal particles and a polymer dispersant, and further contains a polyolefin wax emulsion and an amine, can solve the above problems. That is, the present invention relates to the following [1] and [2].
• a method for producing a printed matter comprising the step of printing the water-based ink containing fine metal particles according to [1] on a substrate to obtain a printed matter in which a metal film is formed on the substrate.
• the present invention it is possible to provide a water-based ink containing fine metal particles that is excellent in document offset resistance and a method for producing a printed matter using the ink containing water-based metal fine particles.
• the water-based ink containing fine metal particles (hereinafter also simply referred to as "ink") of the present invention contains fine metal particles A dispersed with polymer B, polyolefin wax particles C, amine D and water.
• the polyolefin wax contained in the emulsion has a low surface tension, it is likely to bleed out on the surface of the metal film and further crystallize to form a thin layer.
• the amine strongly adsorbs to the metal fine particles, and by maintaining the adsorbed state even after the film is formed on the substrate, the progress of sintering of the metal fine particles is suppressed. Conceivable.
• a uniform and smooth metal film is maintained, and a wax layer having a releasing effect is uniformly formed on the formed uniform and smooth film.
• the polyolefin wax forms a thin layer that exhibits scratch resistance, and the amine maintains a uniform and smooth metal film, resulting in high gloss and suppressing the decrease in gloss over time. It is believed that a metal film is obtained.
• Metals (metal atoms) constituting the fine metal particles A include Group 4 transition metals such as titanium and zirconium; Group 5 transition metals such as vanadium and niobium; and Group 6 transition metals such as chromium, molybdenum and tungsten.
• Group 7 transition metals such as manganese, technetium and rhenium; Group 8 transition metals such as iron and ruthenium; Group 9 transition metals such as cobalt, rhodium and iridium; Group 10 transition metals, Group 11 transition metals such as copper, silver, and gold, Group 12 transition metals such as zinc and cadmium, Group 13 metals such as aluminum, gallium, and indium, germanium, tin, and lead.
• Group 14 metals such as One of the metals constituting the fine metal particles A may be used as a single metal, or two or more of them may be used in combination as an alloy.
• the metal constituting the metal fine particles A is preferably at least one selected from gold, silver, copper, platinum, aluminum, titanium, iron, nickel, zinc, and tin. From the viewpoint of further improving the storage stability of the metal fine particles A and the glossiness of the metal film, it more preferably contains at least one selected from gold, silver and copper, and further improves the glossiness of the metal film. Since various metallic colors can be expressed by combining with colored inks, silver is more preferable, and silver is more preferable. The type of metal can be confirmed by high frequency inductively coupled plasma emission spectrometry.
• the total content of gold, silver, and copper in the metal fine particles A is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass, from the viewpoint of further improving the glossiness of the metal film. Above, more preferably 98% by mass or more, more preferably substantially 100% by mass.
• the content of silver in the fine metal particles A is preferably 80% by mass or more, more preferably 90% by mass or more, because it further improves the glossiness of the metal film and can express various metallic colors by combining with colored inks. , more preferably 95% by mass or more, more preferably 98% by mass or more, and still more preferably substantially 100% by mass.
• substantially 100% by mass means that unintentionally contained components may be included. Components that are unintentionally included include, for example, unavoidable impurities.
• the content of the fine metal particles A in the ink according to the present invention is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass, from the viewpoint of further improving the glossiness and concealability of the metal film. % or more, and from the viewpoint of further improving the gloss stability of the metal film, it is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and still more preferably 12% by mass or less. , and more preferably 8% by mass or less.
• the metal fine particles A according to the present invention are dispersed with a polymer B from the viewpoint of improving the dispersion stability and document offset resistance of the metal fine particles A.
• the polymer B preferably contains structural units derived from the monomer (b-1) having a carboxy group and the monomer (b- 2) is a vinyl-based polymer containing structural units derived from The vinyl-based polymer may be a block copolymer, a random copolymer, or an alternating copolymer.
• Monomer (b-1) having a carboxy group includes unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid and 2-methacryloyloxymethylsuccinic acid; unsaturated dicarboxylic acids such as maleic acid, itaconic acid, fumaric acid and citraconic acid. etc.
• the unsaturated dicarboxylic acid may be an anhydride.
• Monomer (b-1) may be used alone or in combination of two or more.
• Monomer (b-1) is preferably at least one selected from (meth)acrylic acid and maleic acid, and more preferably ( meth) acrylic acid.
• (meth)acrylic acid means at least one selected from acrylic acid and methacrylic acid.
• (Meth)acrylic acid” below has the same meaning.
• Examples of the monomer (b-2) include polyalkylene glycol (meth)acrylates, alkoxypolyalkyleneglycol (meth)acrylates, phenoxypolyalkyleneglycol (meth)acrylates, and the like.
• the monomer (b-2) may be used alone or in combination of two or more.
• “(meth)acrylate” is at least one selected from acrylate and methacrylate.
• “(Meth)acrylate” below has the same meaning.
• Monomer (b-2) is preferably at least one selected from polyalkylene glycol (meth)acrylates and alkoxypolyalkylene glycol (meth)acrylates, from the viewpoint of further improving the dispersion stability and document offset resistance of fine metal particles A. It is one type, more preferably alkoxypolyalkylene glycol (meth)acrylate, and still more preferably alkoxypolyethylene glycol (meth)acrylate.
• the number of carbon atoms in the alkoxy group of the alkoxypolyalkylene glycol (meth)acrylate is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, from the same viewpoint as described above.
• the alkoxy polyalkylene glycol (meth)acrylates include methoxy polyalkylene glycol (meth) acrylate, ethoxy polyalkylene glycol (meth) acrylate, propoxy polyalkylene glycol (meth) acrylate, butoxy polyalkylene glycol (meth) acrylate, octoxy Polyalkylene glycol (meth)acrylate and the like are included.
• the polyoxyalkylene group of the monomer (b-2) preferably contains an alkylene oxide-derived unit having 2 to 4 carbon atoms.
• the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide.
• the polyoxyalkylene group more preferably contains an ethylene oxide-derived unit from the viewpoint of further improving the dispersion stability and document offset resistance of the metal fine particle A.
• the number of units derived from alkylene oxide in the polyoxyalkylene group (hereinafter also referred to as "n") is preferably 2 or more, and It is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, and is preferably 100 or less, more preferably 70 or less, still more preferably 50 or less, still more preferably 40 or less.
• the polyoxyalkylene group may be a copolymer containing units derived from ethylene oxide and units derived from propylene oxide, from the viewpoint of further improving the dispersion stability and document offset resistance of the metal fine particles A.
• the molar ratio [EO/PO] (hereinafter also referred to as “molar ratio [EO/PO]”) between the ethylene oxide-derived units (EO) and the propylene oxide-derived units (PO) is preferably 60/40 or more, More preferably 65/35 or more, still more preferably 70/30 or more, and preferably 90/10 or less, more preferably 85/15 or less, still more preferably 80/20 or less.
• the copolymer containing ethylene oxide-derived units and propylene oxide-derived units may be a block copolymer, a random copolymer, or an alternating copolymer.
• b-2 Specific examples include Shin-Nakamura Chemical Co., Ltd. NK Ester AM-90G, NK Ester AM-130G, NK Ester AM-230G, AMP-20GY, M- 20G, same M-40G, same M-90G, same M-230G, etc.; PME-400, PME-1000, PME-4000, PP-500, PP-800, PP-1000, AP-150, AP-400, AP-550, 50PEP-300, 50POEP-800B, 43PAPE-600B and the like.
• the polymer B comprises a monomer (b-2) having a structural unit derived from the monomer (b-1) having a carboxy group and a polyoxyalkylene group.
• the vinyl polymer preferably further contains a structural unit derived from the hydrophobic monomer (b-3).
• hydrophobic monomer means that the amount of the monomer dissolved in 100 g of deionized water at 25° C. until saturation is less than 10 g.
• the dissolved amount of the monomer (b-3) is preferably 5 g or less, more preferably 1 g or less, from the same viewpoint as described above.
• Examples of the monomer (b-3) include styrenic monomers, (meth)acrylic acid esters, and the like.
• Monomer (b-3) may be used alone or in combination of two or more.
• Styrene-based monomers include styrene, ⁇ -methylstyrene, 2-methylstyrene, 4-vinyltoluene (4-methylstyrene), and divinylbenzene from the viewpoint of further improving the dispersion stability and document offset resistance of the metal fine particles A.
• Styrene and styrene derivatives such as (vinylstyrene) are preferred, and styrene and ⁇ -methylstyrene are more preferred.
• (Meth)acrylic acid esters include aromatic group-containing (meth)acrylic acid esters and (meth)acrylic acid esters having a hydrocarbon group derived from an aliphatic alcohol.
• aromatic group-containing (meth)acrylates phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl (meth)acrylate are used from the viewpoint of further improving the dispersion stability and document offset resistance of fine metal particles A. etc. are preferred, and benzyl (meth)acrylate is more preferred.
• the (meth)acrylic acid ester having a hydrocarbon group derived from an aliphatic alcohol is preferably an aliphatic alcohol having 1 to 22 carbon atoms from the viewpoint of further improving the dispersion stability and document offset resistance of the fine metal particles A. It has a hydrocarbon group derived from.
• Examples of (meth)acrylic acid esters having a hydrocarbon group derived from an aliphatic alcohol include (meth)acrylates having a straight-chain alkyl group, (meth)acrylates having a branched-chain alkyl group, and alicyclic alkyl groups. (Meth)acrylates are mentioned.
• (Meth)acrylates having a linear alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, octyl (meth)acrylate, decyl (Meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate and the like.
• (Meth)acrylates having a branched alkyl group include isopropyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isopentyl (meth)acrylate, isooctyl (meth)acrylate, and isodecyl (meth)acrylate. , isododecyl (meth)acrylate, isostearyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and the like. Cyclohexyl (meth)acrylate etc. are mentioned as (meth)acrylate which has an alicyclic alkyl group.
• the (meth)acrylic acid ester is preferably a (meth)acrylic acid ester having a hydrocarbon group derived from an aliphatic alcohol, more preferably a (meth)acrylic acid having an alkyl group having 6 to 10 carbon atoms is an ester.
• Monomer (b-3) is preferably at least one selected from styrene-based monomers and (meth)acrylic acid esters, and more preferably, from the viewpoint of further improving the dispersion stability and document offset resistance of fine metal particles A.
• the vinyl-based polymer as the polymer B contains structural units derived from the monomer (b-1) and structural units derived from the monomer (b-2) and does not contain structural units derived from the monomer (b-3), during the production of the polymer B
• the content of the monomers (b-1) and (b-2) in the raw material monomer the content as an unneutralized amount; the same shall apply hereinafter
• the structural unit derived from the monomer (b-1) in the polymer B is as follows.
• the content of the monomer (b-1) is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, still more preferably 50 mol% or more, More preferably 60 mol% or more, and preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less, still more preferably 75 mol% or less.
• the content of the monomer (b-2) is preferably 10 mol% or more, more preferably 15 mol% or more, still more preferably 20 mol% or more, still more preferably 25 mol% or more, and preferably 90 mol.
• the content molar ratio of the monomer (b-1) and the monomer (b-2) [monomer (b-1)/monomer (b-2)] is preferably 0.5 or more, more preferably 1 or more, and still more preferably It is 1.5 or more, and preferably 5 or less, more preferably 4 or less, still more preferably 3.5 or less, still more preferably 3 or less, still more preferably 2.5 or less.
• the content (content as an unneutralized amount; hereinafter the same) or the content of structural units derived from monomers (b-1) to (b-3) in polymer B is the dispersion stability of metal fine particles A and From the standpoint of further improving the document offset resistance, the following is given.
• the content of the monomer (b-1) is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more, and preferably 40 mol% or less, more preferably 35 mol%.
• the content of the monomer (b-2) is preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 7 mol% or more, and preferably 30 mol% or less, more preferably 20 mol%. % or less, more preferably 15 mol % or less.
• the content of the monomer (b-3) is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 65 mol% or more, and preferably 90 mol% or less, more preferably 85 mol%. % or less, more preferably 80 mol % or less.
• the content molar ratio of the monomer (b-1) and the monomer (b-2) [monomer (b-1)/monomer (b-2)] is preferably 0.5 or more, more preferably 1 or more, and still more preferably It is 1.5 or more, and preferably 3 or less, more preferably 2.5 or less, and still more preferably 2 or less.
• the total content of the constituent units derived from the monomer (b-1) and the constituent units derived from the monomer (b-2) in the polymer B is preferably 8 mol% or more, more preferably 10 mol% or more, still more preferably 15 It is mol % or more, more preferably 20 mol % or more, and preferably 70 mol % or less, more preferably 50 mol % or less, still more preferably 40 mol % or less.
• Polymer B may be synthesized by a known method, or may be a commercially available product.
• Commercially available products of Polymer B include DISPERBYK-190 and 2015 manufactured by BYK.
• the polymer B is preferably a monomer (b- 2) containing a vinyl-based polymer containing a structural unit derived from, more preferably a structural unit derived from at least one selected from (meth)acrylic acid and maleic acid as the monomer (b-1), and the monomer (b-2 ) contains a vinyl-based polymer containing a structural unit derived from an alkoxypolyalkylene glycol (meth) acrylate, and more preferably a structure derived from at least one selected from (meth) acrylic acid and maleic acid as the monomer (b-1) a unit, a structural unit derived from an alkoxypolyalkylene glycol (meth)acrylate as the monomer (b-2), and a structural unit derived from at least one selected from styrene and styrene derivatives as the monomer (b-3).
• system polymer more preferably a structural unit derived from at least one selected from (meth) acrylic acid and maleic acid as the monomer (b-1), and an alkoxy (polyethylene glycol / polypropylene glycol) as the monomer (b-2) (Meth) acrylate (where n is 2 or more and 100 or less, the molar ratio [EO/PO] is 60/40 or more and 90/10 or less)-derived structural units, and styrene and styrene derivatives as the monomer (b-3) and a structural unit derived from at least one selected.
• the content of the vinyl-based polymer containing the structural unit derived from the monomer (b-1) having a carboxyl group in the polymer B and the structural unit derived from the monomer (b-2) having a polyoxyalkylene group is the dispersion of the fine metal particles A.
• the content 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 still more preferably substantially 100% by mass.
• substantially 100% by mass means that unintentionally contained components may be included.
• the unintentionally included component means that, for example, a polymer B component other than the vinyl-based polymer included in the vinyl-based polymer may be included.
• a structural unit derived from the monomer (b-1) having a carboxy group in the polymer B, a structural unit derived from the monomer (b-2) having a polyoxyalkylene group, and a structural unit derived from the hydrophobic monomer (b-3) From the viewpoint of further improving the dispersion stability and document offset resistance of the fine metal particles A, the content of the vinyl polymer is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. , more preferably 98% by mass or more, more preferably substantially 100% by mass.
• substantially 100% by mass means that unintentionally contained components may be included.
• the unintentionally included component means that, for example, a polymer B component other than the vinyl-based polymer included in the vinyl-based polymer may be included.
• a structural unit derived from at least one selected from (meth)acrylic acid and maleic acid as the monomer (b-1) in the polymer B, and a structural unit derived from an alkoxypolyalkylene glycol (meth)acrylate as the monomer (b-2). is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass, from the viewpoint of further improving the dispersion stability and document offset resistance of the fine metal particles A. Above, more preferably 98% by mass or more, more preferably substantially 100% by mass.
• substantially 100% by mass means that unintentionally contained components may be included.
• the unintentionally included component means that, for example, a polymer B component other than the vinyl-based polymer included in the vinyl-based polymer may be included.
• substantially 100% by mass means that unintentionally contained components may be included.
• the unintentionally included component means that, for example, a polymer B component other than the vinyl-based polymer included in the vinyl-based polymer may be included.
• the content of the vinyl-based polymer containing a seed-derived structural unit is preferably at least 80% by mass, more preferably at least 90% by mass.
• substantially 100% by mass means that unintentionally contained components may be included.
• the unintentionally included component means that, for example, a polymer B component other than the vinyl-based polymer included in the vinyl-based polymer may be included.
• the number average molecular weight Mn of the polymer B is preferably 1,000 or more, more preferably 2,000 or more, and still more preferably 3,000 or more, from the viewpoint of further improving the dispersion stability of the metal fine particles A. From the viewpoint, it is preferably 100,000 or less, more preferably 50,000 or less, still more preferably 30,000 or less, even more preferably 10,000 or less, and even more preferably 6,000 or less.
• the number average molecular weight Mn is measured by the method described in Examples.
• the acid value of the polymer B is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 15 mgKOH/g or more, from the viewpoint of further improving the dispersion stability of the metal fine particles A. , preferably 800 mgKOH/g or less, more preferably 600 mgKOH/g or less, still more preferably 400 mgKOH/g or less, still more preferably 200 mgKOH/g or less, still more preferably 120 mgKOH/g or less, still more preferably 100 mgKOH/g or less, still more preferably is 70 mgKOH/g or less, more preferably 50 mgKOH/g or less, still more preferably 40 mgKOH/g or less, still more preferably 30 mgKOH/g or less.
• the acid value of polymer B can be measured by the method described in Examples, but can also be calculated from the mass ratio of the constituent monomers.
• the content of the polymer B in the ink according to the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably It is 0.3% by mass or more, more preferably 0.4% by mass or more, and from the viewpoint of further improving the dispersion stability of the metal fine particles A and the glossiness of the metal film, preferably 5% by mass or less, more preferably 3 % by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.
• the mass ratio of the content of the polymer B to the total content of the polymer B and the fine metal particles A in the ink according to the present invention [polymer B/(fine metal particles A + polymer B)] further improves the dispersion stability of the fine metal particles A. is preferably 0.01 or more, more preferably 0.03 or more, and still more preferably 0.04 or more from the viewpoint of increasing the is 0.3 or less, more preferably 0.2 or less, and still more preferably 0.15 or less.
• the mass ratio [polymer B/(metal fine particle A + polymer B)] is the mass of metal fine particle A and polymer B measured by the method described in Examples using a simultaneous differential thermogravimetric analyzer (TG/DTA). calculated from
• the ink according to the present invention contains polyolefin wax particles C from the viewpoint of further improving document offset resistance and scratch resistance.
• the term “wax” refers to an organic substance having an alkyl group that is solid or semi-solid at room temperature, has a melting point of 50° C. or more and 160° C. or less, and melts without decomposition when heated to +10° C. °C high temperature of 10 Pa ⁇ s or less.
• the viscosity is, for example, viscosity measured under the following conditions.
• Measuring instrument Rheometer (MCR302, manufactured by Anton-par) Measurement mode: Shear test Measuring jig: ⁇ Upper> Cone plate (25 mm), ⁇ Lower> Disposable plate Measurement sample: 1 g of wax Measurement temperature: Melting point +10°C Shear rate: 100 (1/s)
• Polyolefin wax particles C preferably contain at least one selected from polyethylene wax particles and polypropylene wax particles, and more preferably contain polyethylene wax particles, from the viewpoint of further improving the document offset resistance and the scratch resistance of the metal film. .
• the polyolefin wax particles C can be used singly or in combination of two or more.
• the polyolefin wax particles C are in the form of an emulsion containing the polyolefin wax particles C (hereinafter also referred to as "wax emulsion C") from the viewpoint of further improving the productivity of the ink. It is preferred to use
• the content of the polyolefin wax particles C in the wax emulsion C is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more, from the viewpoint of further improving productivity. From the viewpoint of further improving the dispersion stability of the ink, the content is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
• the emulsion containing polyolefin wax particles C is preferably nonionic from the viewpoint of further improving document offset resistance, dispersion stability and abrasion resistance.
• nonionic refers to an agent that does not ionize in water to form ions.
• the average particle size of the polyolefin wax particles C is preferably 20 nm or more, more preferably 40 nm or more, still more preferably 50 nm or more, still more preferably 55 nm or more, from the viewpoint of further improving the document offset resistance and the scratch resistance of the metal film. and is preferably 250 nm or less, more preferably 180 nm or less, still more preferably 150 nm or less, even more preferably 100 nm or less, still more preferably 75 nm or less, from the viewpoint of further improving the glossiness and gloss stability of the metal film.
• the average particle size of the polyolefin wax particles C can be measured by the method described in Examples.
• the melting point of the polyolefin wax particles C is preferably 80° C. or higher, more preferably 100° C. or higher, still more preferably 120° C. or higher, still more preferably 130° C., from the viewpoint of further improving the document offset resistance and the scratch resistance of the metal film. from the viewpoint of further improving the glossiness of the metal film, the temperature is preferably 160°C or less, more preferably 150°C or less, and even more preferably 145°C or less.
• the melting point of the polyolefin wax particles C can be measured by the method described in Examples.
• the content of the polyolefin wax particles C in the ink according to the present invention is preferably 0.01% by mass or more from the viewpoint of further improving the document offset resistance, the scratch resistance of the metal film, and the gloss stability of the metal film.
• More preferably 0.02% by mass or more, still more preferably 0.03% by mass or more, still more preferably 0.04% by mass or more, from the viewpoint of further improving the glossiness and gloss stability of the metal film preferably is 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, and even more preferably 0.1% by mass or less.
• the mass ratio of the content of the polyolefin wax particles C to the content of the metal fine particles A in the ink according to the present invention [polyolefin wax particles C/metal fine particles A] further improves the document offset resistance and the abrasion resistance of the metal film. From the viewpoint of increasing the From the viewpoint, it is preferably 0.1 or less, more preferably 0.07 or less, still more preferably 0.05 or less, and still more preferably 0.02 or less.
• the ink according to the present invention contains amine D from the viewpoint of further improving the document offset resistance, the glossiness of the metal film, and the gloss stability of the metal film.
• Examples of the amine D include alkylamines such as propylamine, butylamine, hexylamine, diethylamine, dipropylamine, dimethylethylamine, diethylmethylamine and triethylamine, ethanolamine, N-methylethanolamine and N,N-dimethylethanolamine.
• alkylamines such as propylamine, butylamine, hexylamine, diethylamine, dipropylamine, dimethylethylamine, diethylmethylamine and triethylamine, ethanolamine, N-methylethanolamine and N,N-dimethylethanolamine.
• N,N-diethylethanolamine diethanolamine, N-methyldiethanolamine, triethanolamine, propanolamine, isopropanolamine, N,N-dimethylpropanolamine, butanolamine, alkanolamine such as hexanolamine, ethylenediamine, triethylenediamine, tetra Aliphatic amines such as (poly)alkylenepolyamines such as methylethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine; alicyclic amines such as piperidine, pyrrolidine, N-methylpyrrolidine, and morpholine aromatic amines such as aniline, N-methylaniline, toluidine, anisidine and phenetidine; aralkylamines such as benzylamine and N-methylbenzylamine;
• Amine D is one or more aliphatic selected from alkylamines, alkanolamines, and (poly)alkylenepolyamines, from the viewpoint of further improving the document offset resistance, the glossiness of the metal film, and the gloss stability of the metal film.
• It preferably contains an amine, more preferably an aliphatic amine having 12 or less carbon atoms, more preferably an aliphatic amine having 6 or less carbon atoms, still more preferably an aliphatic amine having 6 or less carbon atoms and primary and secondary, and further Preferred are primary and secondary alkylamines having 6 or less carbon atoms or primary and secondary alkanolamines having 6 or less carbon atoms and more preferably primary alkanolamines having 6 or less carbon atoms.
• Amine D includes propylamine, butylamine, hexylamine, diethylamine, dipropylamine, dimethylethylamine, diethylmethylamine, and triethylamine, ethanolamine, N-methylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, propanolamine, isopropanolamine, N,N-dimethylpropanol
• One or more selected from amine, butanolamine, hexanolamine, ethylenediamine, triethylenediamine, tetramethylethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine are preferable, and butylamine, ethanolamine, One or more selected from N,N-dimethylethanolamine, isopropanolamine, ethylenediamine, and
• the above are more preferable, more preferably one or more selected from butylamine, ethanolamine, isopropanolamine, and ethylenediamine, more preferably one or more selected from butylamine, ethanolamine, and isopropanolamine, and selected from ethanolamine and isopropanolamine.
• One or more are more preferred, and isopropanolamine is even more preferred.
• Amine D can be used individually by 1 type or in combination of 2 or more types.
• the content of amine D in the ink according to the present invention is preferably 0.05% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of further improving the document offset resistance, the glossiness of the metal film, and the gloss stability of the metal film. is 0.1% by mass or more, more preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.4% by mass or more, further improving the dispersion stability of the metal fine particles A from the viewpoint of increasing the content, the content is preferably 2% by mass or less, more preferably 1% by mass or less, even more preferably 0.8% by mass or less, and even more preferably 0.6% by mass or less.
• the mass ratio of the content of the polyolefin wax particles C to the content of the amine D in the ink according to the present invention is from the viewpoint of further improving the document offset resistance and the abrasion resistance of the metal film. Therefore, it is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.08 or more, and still more preferably 0.1 or more, from the viewpoint of further improving the glossiness and gloss stability of the metal film , preferably 20 or less, more preferably 10 or less, still more preferably 2 or less, still more preferably 1 or less, still more preferably 0.5 or less, still more preferably 0.35 or less, still more preferably 0.2 or less.
• the smoothness and uniformity of the metal film can be improved.
• the thickness of the wax layer that bleeds out becomes more appropriate, and document offset resistance, scratch resistance, glossiness, and gloss stability can be further improved.
• the mass ratio of the content of amine D to the content of fine metal particles A in the ink according to the present invention determines the document offset resistance, the glossiness of the metal film, and the gloss stability of the metal film. from the viewpoint of further improving the metal fine particles From the viewpoint of further improving the dispersion stability of A, it is preferably 1 or less, more preferably 0.2 or less, and even more preferably 0.15 or less.
• the mass ratio of the content of amine D to the content of polymer B in the ink according to the present invention improves the document offset resistance, the glossiness of the metal film, and the gloss stability of the metal film. From the viewpoint of improvement, it is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, still more preferably 0.5 or more, and the glossiness of the metal film and the dispersion stability of the metal fine particles A It is preferably 3 or less, more preferably 2 or less, and still more preferably 1.5 or less from the viewpoint of further improving the properties.
• the ink according to the present invention preferably contains a solvent E from the viewpoint of improving the dispersion stability of the metal fine particles A and improving the ejection stability of the ink.
• Solvent E is not particularly limited, and a water-soluble organic solvent can be used. Amides, sulfur-containing compounds and the like can be mentioned. Solvent E can be used individually by 1 type or in combination of 2 or more types.
• polyhydric alcohols examples include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butane.
• polyhydric alcohol alkyl ethers examples include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono Butyl ether, dipropylene glycol monobutyl ether, polyethylene glycol dimethyl ether and the like.
• polyhydric alcohol aryl ethers examples include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
• nitrogen-containing heterocyclic compounds include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ⁇ -caprolactam, and ⁇ -butyrolactone. etc.
• amides include formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide and the like.
• sulfur-containing compounds include dimethylsulfoxide, sulfolane, thiodiethanol and the like.
• polyhydric alcohols are preferred from the viewpoint of ink dispersion stability and hydrophilicity, and ethylene glycol, diethylene glycol, propylene glycol, and 1,3-propanediol are more preferred from the viewpoint of ejection stability and drying properties.
• polyhydric alcohol alkyl ethers are preferable, such as diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene More preferred are glycol monobutyl ether, dipropylene glycol monobutyl ether, and polyethylene glycol dimethyl ether.
• polyhydric alcohols and polyhydric alcohol alkyl ethers More preferably used in combination, one or more selected from ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, and diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether , dipropylene glycol monobutyl ether, and polyethylene glycol dimethyl ether.
• the content of the solvent E in the ink according to the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of further improving the dispersion stability of the metal fine particles A and the ejection stability of the ink.
• the content is preferably 20% by mass or more, and from the viewpoint of further improving the glossiness and scratch resistance of the metal film, it is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.
• the ink according to the invention contains water.
• the water content in the ink according to the present invention is preferably 20% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and even more preferably. is 60% by mass or more, and is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less from the viewpoint of further improving ink ejection stability.
• the ink according to the present invention contains, as components other than the above components A to E and water, a fixing aid such as a dispersion of polymer particles, a moisturizing agent, a wetting agent, and a penetrating agent, as long as the effects of the present invention are not impaired. , a surfactant, a viscosity modifier, an antifoaming agent, an antiseptic, an anti-mold agent, an anti-rust agent and the like.
• the ink according to the present invention is prepared by adding and mixing a polymer B as a dispersant, a wax emulsion C, an amine D, water, and optionally a solvent E and the above additives to metal fine particles A prepared in advance by a known method.
• the wax emulsion C, the amine D, water, and if necessary the solvent E is preferably added and mixed.
• the metal fine particle dry powder is obtained by mixing a metal raw material compound, a reducing agent, and a polymer B, reducing the metal raw material compound with a reducing agent, and obtaining a dispersion of fine metal particles dispersed in the polymer B.
• a dispersion of fine particles can be obtained by drying such as by freeze-drying.
• the metal source compound is not particularly limited as long as it is a compound containing the metal that constitutes the fine metal particles A described above.
• the metal source compound include metal salts of inorganic acids or organic acids, metal oxides, metal hydroxides, metal sulfides, metal halides, and the like, including the metals exemplified for the fine metal particles A described above.
• the metal salt include inorganic acid metal salts such as nitrates, nitrites, sulfates, carbonates, ammonium salts, and perchlorates; and organic acid metal salts such as acetates.
• the metal source compounds can be used singly or in combination of two or more.
• 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 preferred.
• the reducing agents may be used singly or in combination of two or more.
• organic reducing agents include alcohols, aldehydes, acids and salts thereof, and amines.
• alcohols include ethylene glycol and propylene glycol.
• Aldehydes include formaldehyde, acetaldehyde, propionaldehyde and the like.
• Acids and salts thereof include ascorbic acid, citric acid, and salts thereof.
• Amines include alkanolamines, alkylamines, (poly)alkylenepolyamines, heterocyclic amines, aromatic amines, aralkylamines, and the like.
• inorganic reducing agents examples include borohydride salts such as sodium borohydride and ammonium borohydride; aluminum hydride salts such as lithium aluminum hydride and potassium aluminum hydride; hydrazines such as hydrazine and hydrazine carbonate; are mentioned.
• 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, and still more preferably 30° C. or higher, from the viewpoint of reducing and uniformizing the particle size of the metal fine particles, From the viewpoint of stably producing fine metal particles, the temperature is preferably 100° C. or lower, more preferably 80° C. or lower, and still more preferably 50° C. or lower.
• the reduction reaction may be performed in an air atmosphere or in an inert gas atmosphere such as nitrogen gas.
• the metal fine particle dispersion is purified before freeze-drying.
• the method for purifying the fine metal particle dispersion is not particularly limited, and examples thereof include membrane treatments such as dialysis and ultrafiltration; centrifugal separation and the like. Among them, membrane treatment is preferred, and dialysis is more preferred, from the viewpoint of efficiently removing impurities.
• membrane treatment is preferred, and dialysis is more preferred, from the viewpoint of efficiently removing impurities.
• regenerated cellulose is preferable.
• the molecular weight cutoff 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, from the viewpoint of efficiently removing impurities. 70,000 or less, more preferably 70,000 or less.
• the ink according to the present invention can be obtained by further adding the various additives described above as necessary and performing a filtration treatment using a filter or the like.
• the average particle size of the fine metal particles A contained in the ink according to the present invention is preferably 20 nm or more, more preferably 30 nm or more, and still more preferably 40 nm or more, from the viewpoint of further suppressing aggregation of the metal fine particles A.
• the thickness is preferably 100 nm or less, more preferably 80 nm or less, and even more preferably 60 nm or less.
• the average particle size of the fine metal particles A can be measured by the method described in Examples.
• the viscosity of the ink according to the present invention at 30° C. is preferably 1 mPa ⁇ s or more, more preferably 1.5 mPa ⁇ s or more, still more preferably 2 mPa ⁇ s or more, from the viewpoint of further suppressing sedimentation of the metal fine particles A. It is preferably 2.5 mPa s or more, and from the viewpoint of further improving the glossiness of the metal film, it is preferably 20 mPa s or less, more preferably 10 mPa s or less, even more preferably 5 mPa s or less, still more preferably 4 mPa. ⁇ It is less than or equal to s.
• the viscosity of the ink is measured by the method described in Examples using an E-type viscometer.
• the ink according to the present invention can form a metal film having excellent document offset resistance, it is particularly suitable for various printing applications such as inkjet printing, flexographic printing, gravure printing, screen printing, offset printing, and dispenser printing. can be used for Above all, the ink according to the present invention is preferably used for inkjet printing because it has excellent ejection reliability as described above.
• the method for producing a printed matter according to the present invention preferably includes a step of printing the water-based ink containing fine metal particles according to the present invention on a substrate to obtain a printed matter having a metal film formed on the substrate. As a result, it is possible to obtain a printed matter on which a metal film having excellent document offset resistance and the like is formed.
• Examples of the substrate include paper; fabric; resin; metal; glass; Examples of the paper substrate include coated paper (coated paper, art paper, etc.), uncoated paper, plain paper, kraft paper, synthetic paper, processed paper, cardboard, and the like.
• the fabric used as the base material includes fabrics made of natural fibers such as cotton, silk, and hemp, synthetic fibers such as rayon fibers, acetate fibers, nylon fibers, and polyester fibers, and blended fabrics made of two or more of these fibers. mentioned.
• resin substrates examples include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polypropylene (PP), polyamide (PA), polyimide (PI), polyvinyl chloride (PVC), poly Synthetic resin films such as methyl methacrylate (PMMA), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), and polycarbonate (PC) can be mentioned.
• metal substrates include substrates using metals such as gold, silver, copper, palladium, platinum, aluminum, nickel, and tin.
• the base material may be a rigid base material or a flexible base material.
• various patterning printing methods such as inkjet printing, flexographic printing, gravure printing, screen printing, offset printing, and dispenser printing are preferably used.
• the amount of the water-based ink containing fine metal particles according to the present invention to be applied to the substrate can be appropriately adjusted according to the size and type of the desired printed matter.
• the present invention further discloses the following embodiments.
• ⁇ 1> A water-based ink containing fine metal particles containing fine metal particles A dispersed with polymer B, polyolefin wax particles C, amine D and water.
• ⁇ 2> A water-based ink containing fine metal particles containing fine metal particles A dispersed with polymer B, polyolefin wax particles C, amine D, and water, The water-based ink containing fine metal particles according to ⁇ 1>, wherein the metal constituting the fine metal particles A contains silver.
• the metal that constitutes the fine metal particles A contains silver, ⁇ 1> or ⁇ 2, wherein the polymer B comprises a vinyl-based polymer containing a structural unit derived from a monomer (b-1) having a carboxy group and a structural unit derived from a monomer (b-2) having a polyoxyalkylene group. > water-based ink containing fine metal particles.
• the polymer B is a structural unit derived from at least one selected from (meth)acrylic acid and maleic acid as the monomer (b-1), and a structural unit derived from alkoxypolyalkylene glycol (meth)acrylate as the monomer (b-2).
• the water-based ink containing fine metal particles according to any one of ⁇ 1> to ⁇ 3>, which contains a vinyl polymer containing ⁇ 5>
• the polymer B comprises a structural unit derived from a monomer (b-1) having a carboxy group, a structural unit derived from a monomer (b-2) having a polyoxyalkylene group, and a structural unit derived from a hydrophobic monomer (b-3).
• the water-based ink containing fine metal particles according to any one of ⁇ 1> to ⁇ 3>, which contains a vinyl polymer containing ⁇ 6>
• the polymer B has a structural unit derived from at least one selected from (meth)acrylic acid and maleic acid as the monomer (b-1), a structural unit derived from an alkoxypolyalkylene glycol (meth)acrylate as the monomer (b-2), and a vinyl-based polymer containing a structural unit derived from at least one selected from styrene and styrene derivatives as the monomer (b-3).
• the polymer B has a structural unit derived from at least one selected from (meth)acrylic acid and maleic acid as the monomer (b-1), and an alkoxy (polyethylene glycol/polypropylene glycol) (meth)acrylate (meth)acrylate as the monomer (b-2).
• n is 2 or more and 100 or less
• the molar ratio [EO/PO] is 60/40 or more and 90/10 or less
• at least one selected from styrene and styrene derivatives as the monomer (b-3).
• the water-based ink containing fine metal particles according to ⁇ 5> or ⁇ 6>, which contains a vinyl-based polymer containing a structural unit derived from.
• the solvent E is one or more selected from ethylene glycol, diethylene glycol, propylene glycol, and 1,3-propanediol, and diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and dipropylene.
• the water-based ink containing fine metal particles according to ⁇ 12> or ⁇ 13>, wherein one or more selected from glycol monobutyl ether and polyethylene glycol dimethyl ether are used in combination.
• the water-based ink containing fine metal particles according to any one of ⁇ 1> to ⁇ 14>, wherein the content of water in the water-based ink containing fine metal particles is 20% by mass or more and 85% by mass or less.
• the content of the fine metal particles A in the water-based ink containing fine metal particles is 1% by mass or more and 30% by mass or less, the content of the polymer B is 0.1% by mass or more and 5% by mass or less, and the content of the polyolefin wax particles C is 0%.
• the content of the vinyl polymer containing the structural unit derived from the monomer (b-1) having a carboxyl group and the structural unit derived from the monomer (b-2) having a polyoxyalkylene group in the polymer B is 80% by mass or more.
• ⁇ 19> Including a structural unit derived from the monomer (b-1) having a carboxy group in polymer B, a structural unit derived from the monomer (b-2) having a polyoxyalkylene group, and a structural unit derived from the hydrophobic monomer (b-3)
• the water-based ink containing fine metal particles according to any one of ⁇ 5> to ⁇ 18>, wherein the content of the vinyl polymer is 80% by mass or more.
• ⁇ 20> A structural unit derived from at least one selected from (meth)acrylic acid and maleic acid as the monomer (b-1) in the polymer B and a structural unit derived from an alkoxypolyalkylene glycol (meth)acrylate as the monomer (b-2)
• the water-based ink containing fine metal particles according to any one of ⁇ 4> to ⁇ 19>, wherein the content of the vinyl polymer is 80% by mass or more.
• ⁇ 22> The water-based ink containing fine metal particles according to any one of ⁇ 1> to ⁇ 21>, wherein the amine D contains one or more aliphatic amines selected from alkylamines, alkanolamines, and (poly)alkylenepolyamines.
• a method for producing a printed matter comprising a step of printing the water-based ink containing fine metal particles according to any one of ⁇ 1> to ⁇ 22> onto a substrate to obtain a printed matter having a metal film formed on the substrate.
• ⁇ 24> The method for producing a printed matter according to ⁇ 23>, wherein a method for printing the ink onto the substrate is an inkjet printing method.
• GPC device "HLC-8320GPC” manufactured by Tosoh Corporation Column: “TSKgel SuperAWM-H, TSKgel SuperAW3000, TSKgel guardcolumn Super AW-H” manufactured by Tosoh Corporation Eluent: a solution in which phosphoric acid and lithium bromide were dissolved in N,N-dimethylformamide at concentrations of 60 mmol/L and 50 mmol/L, respectively Flow rate: 0.5 mL/min Standard material: monodisperse polystyrene kit manufactured by Tosoh Corporation “PStQuick B (F-550, F-80, F-10, F-1, A-1000), PStQuick C (F-288, F-40, F-4 , A-5000, A-500)”
• PStQuick B F-550, F-80, F-10, F-1, A-1000
• PStQuick C F-288, F-40, F-4 , A-5000, A-500
• Average particle size of polyolefin wax particles C in wax emulsion Using a laser particle analysis system "ELS-8000" (manufactured by Otsuka Electronics Co., Ltd.), the particle size is measured by a dynamic light scattering method and analyzed by a cumulant method. Calculated by The measurement conditions are a temperature of 25° C., an angle between the incident light and the detector of 90°, and the number of accumulations of 100 times, and the refractive index of water (1.333) is input as the refractive index of the dispersion solvent.
• the sample is weighed into a screw tube (No. 5 manufactured by Maruem Co., Ltd.), water is added so that the solid content concentration becomes 5 ⁇ 10 -3 % by mass, and the sample is stirred at 25 ° C. using a magnetic stirrer. Stir for 1 hour and use.
• Preparation Example 2 (Preparation of Polymer B-2) A thermometer, a dropping funnel (1) with a 200 mL nitrogen bypass, a dropping funnel (2) with a 50 mL nitrogen bypass, and a 1000 mL four-necked round-bottomed flask equipped with a reflux device were charged with 100 g of ion-exchanged water. The mixture was vigorously stirred with a tick stirrer, and the internal temperature of the flask was heated to 80° C. in an oil bath. Separately, nitrogen bubbling was performed for 10 minutes. After that, methoxypolyethylene glycol (EO23 mol) acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.
• N- Ester AM-230G 87 g, 98% acrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) 13 g, 3-mercapto 2.0 g of propionic acid (special grade reagent manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was dissolved in a poly beaker and put into a dropping funnel (1). Further, 20 g of ion-exchanged water and 2 g of ammonium peroxodisulfate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) were dissolved in a poly beaker and put into a dropping funnel (2).
• Production Example 1 (Production of Metal Fine Particle Dry Powder 1)
• 10 g of silver oxide manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., special grade
• 1.6 g of polymer B-1 1.6 g
• propylene glycol as a reducing agent manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., special grade
• the obtained mixed solution is heated using a water bath at 40°C, and after the mixed solution reaches 40°C, it is stirred for 1 hour, and then air-cooled to form a dark brown dispersion containing dispersed silver fine particles. got a body
• This tube was immersed in 5 L of deionized water in a 5 L glass beaker and stirred for 1 hour while maintaining the water temperature at 20-25°C.
• the purified dispersion is dried using a freeze dryer (manufactured by Tokyo Rikakikai Co., Ltd., model: FDU-2110) equipped with a dry chamber (manufactured by Tokyo Rikakikai Co., Ltd., model: DRC-1000). Freezing at 25° C. for 1 hour, reducing pressure at ⁇ 10° C. for 9 hours, reducing pressure at 25° C. for 5 hours, and freeze-drying at a reduced pressure of 5 Pa), metal fine particle dry powder 1 was obtained.
• Production Example 2 (Production of Metal Fine Particle Dry Powder 2)
• Example 1 In a 500 mL polyethylene beaker, 5.5 g of metal fine particle dry powder 1, 68.9 g of ion-exchanged water, ( ⁇ ) -1-amino-2-propanol (isopropanolamine, Fujifilm Wako Pure Chemical Industries, Ltd.) as amine D ), 20 g of propylene glycol as solvent E, 5 g of "Hi-solve MPM” (polyethylene glycol dimethyl ether, manufactured by Toho Chemical Industry Co., Ltd.), and 0.14 g of wax emulsion C-1 were added and stirred with a magnetic stirrer.
• the mixture was dispersed for 3 hours with an ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, model: US-3001). Thereafter, filtration was performed using a 5 ⁇ m disposable membrane filter (Minisart, manufactured by Sartorius) to obtain a water-based ink containing fine metal particles.
• Table 1 shows the average particle size of the fine metal particles A in the obtained ink and the viscosity of the obtained ink. The following evaluations were performed using the obtained ink. Results are shown in Tables 1 and 2.
• Examples 2-16, and Comparative Examples 1-4 Water-based metal microparticles were prepared in the same manner as in the production of the ink of Example 1, except that the type of metal microparticle dry powder, polymer B, wax emulsion C, amine D, or solvent E, or the composition of the ink was changed according to Table 1. A contained ink was obtained. Table 1 shows the average particle size of the fine metal particles A in the obtained ink and the viscosity of the obtained ink. The following evaluations were performed using each obtained ink. Results are shown in Tables 1 and 2. Table 3 shows the details of the wax emulsion C used.
• 8° gloss is a value obtained by subtracting SCE (diffuse reflection light only) from SCI (including specular reflection) and converting it into glossiness equivalent, which corresponds to glossiness at a specular reflection angle of 8°. .
• the larger the 8° gloss value the better the metallicity of the metal film.
• 24 hours after the ink coating the 8° gloss of the coating film was measured at three points, and the average value was obtained.
• a value was calculated by subtracting the 8° gloss 30 minutes after coating from the 8° gloss 24 hours after coating, and the gloss change was evaluated. The closer the numerical value is to 0, the less the change in glossiness is and the better it is.
• C One or more out of 10 samples produced a peeling sound during peeling, and image defects were observed in an area less than 1/20 of the total area of the image portions of 10 samples (20 sheets of paper).
• D One or more of the 10 samples produced a peeling sound during peeling, and an image defect was observed in an area of 1/20 or more and less than 1/10 of the total area of the image portion of the 10 samples (20 sheets of paper).
• E At least 1 out of 10 samples produced a peeling sound during peeling, and image loss was observed in an area of 1/10 or more of the total area of the image portions of 10 samples (20 sheets of paper).

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

Priority Applications (2)

Applications Claiming Priority (1)

Publications (1)

Family

ID=86730040

Family Applications (1)

Country Status (2)

Citations (6)

• 2021
  • 2021-12-09 WO PCT/JP2021/045366 patent/WO2023105716A1/ja not_active Ceased
  • 2021-12-09 JP JP2023565807A patent/JPWO2023105716A1/ja active Pending

Patent Citations (6)

Also Published As

Similar Documents

Legal Events