WO2018198722A1 - Encre, procédé de formation d'image, objet formé par image - Google Patents

Encre, procédé de formation d'image, objet formé par image Download PDF

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Publication number
WO2018198722A1
WO2018198722A1 PCT/JP2018/014699 JP2018014699W WO2018198722A1 WO 2018198722 A1 WO2018198722 A1 WO 2018198722A1 JP 2018014699 W JP2018014699 W JP 2018014699W WO 2018198722 A1 WO2018198722 A1 WO 2018198722A1
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WIPO (PCT)
Prior art keywords
group
ink
silver nanoparticles
resin
electron
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PCT/JP2018/014699
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English (en)
Japanese (ja)
Inventor
恒雄 柏木
英也 三輪
中林　亮
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コニカミノルタ株式会社
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Priority to JP2019514342A priority Critical patent/JPWO2018198722A1/ja
Publication of WO2018198722A1 publication Critical patent/WO2018198722A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • 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

Definitions

  • the present invention relates to an ink, an image forming method, and an image formed product.
  • Metallic luster has been a symbol of wealth since ancient times, and it was easy to catch a glance, so it was highly valuable.
  • foil pressing for attaching a metal foil to a substrate has been the mainstream.
  • digital printing there has been an increasing need to impart a metallic gloss to printed matter by digital printing. For example, if it becomes possible to form a printed material with a metallic gloss by digital printing such as an inkjet method, printed materials with various designs can be produced in small lots on demand.
  • Patent Document 1 discloses an ink using an aqueous metal colloid as a metal pigment.
  • an aqueous silver colloid is comparatively easy to synthesize and has a relatively high stability, so that use as a metal pigment is being studied.
  • an ink using water-dispersed silver nanoparticles as a pigment is preferable for improving the working environment because it can reduce the problem of volatile organic solvents.
  • Patent Documents 2 and 3 attempt to add a water-soluble or organic solvent-soluble binder resin to the ink in order to improve the adhesion of silver nanoparticles.
  • Patent Documents 2 and 3 attempt to prevent silver discoloration by adding a discoloration inhibitor to the ink.
  • Non-Patent Document 1 discloses a surface treatment for increasing the work function of the silver surface by molecular adsorption.
  • Non-Patent Document 1 is knowledge regarding a silver electrode of a photoelectric element, and is not intended for silver nanoparticles dispersed in ink or the like, and there is no knowledge regarding prevention of silver discoloration.
  • the present invention has been made in view of the above problems, and in an ink containing silver nanoparticles, an anti-discoloring agent, and a binder resin, the discoloration of the image is prevented while maintaining the glitter of silver. It is an object of the present invention to provide an ink capable of enhancing adhesion and water resistance, an image forming method using the ink, and an image formed product formed using the ink.
  • An ink containing silver nanoparticles, a polymer dispersant adsorbed on the surface of the silver nanoparticles, an anti-discoloring agent, an emulsion resin, and water The anti-discoloring agent has the following formula (I): (Where Z represents a thiol group or a carboxyl group, n is 1 or 2, R 1 represents an aromatic ring substituted with an electron-withdrawing group, a non-aromatic linear, branched or cyclic hydrocarbon group, or an electron-withdrawing substituted or unsubstituted nitrogen-containing heterocyclic ring.
  • the electron withdrawing group is at least one of a nitro group, a cyano group, an amide group, an ester group, a carboxyl group, and a halogenated hydrocarbon group)
  • Ink represented by [2]
  • An image forming method comprising a step of applying the ink according to [1] or [2] to a surface of a substrate to form a metallic gloss layer.
  • the image forming method according to [3] wherein the ink is applied by an inkjet method.
  • the anti-discoloring agent has the following formula (I): (Where Z represents a thiol group or a carboxyl group, n is 1 or 2, R 1 represents an aromatic ring substituted with an electron-withdrawing group, a non-aromatic linear, branched or cyclic hydrocarbon group, or an electron-withdrawing substituted or unsubstituted nitrogen-containing heterocyclic ring. Represent, The electron withdrawing group is at least one of a nitro group, a cyano group, an amide group, an ester group, a carboxyl group, and a halogenated hydrocarbon group)
  • An image formed product represented by
  • an ink containing silver nanoparticles, a discoloration inhibitor, and a binder resin discoloration can be prevented while maintaining silver glitter, and image adhesion and water resistance can be improved.
  • Ink, an image forming method using the ink, and an image formed product formed using the ink are provided.
  • the present inventors have intensively studied in view of the above problems, and in an ink for forming a metallic luster layer containing silver nanoparticles comprising a metal containing silver element, the ink is represented by the following formula (I) as a silver discoloration preventing agent.
  • Ink containing an emulsion resin which is a water-dispersed resin as a binder resin, can prevent discoloration and improve image adhesion and water resistance while maintaining silver glitter. I found.
  • R 1 represents an aromatic ring or a non-aromatic linear, branched or cyclic hydrocarbon group substituted with an electron-withdrawing group, or an electron-withdrawing substituted or unsubstituted nitrogen-containing heterocyclic ring.
  • the electron withdrawing group is a nitro group, a cyano group, an amide group, an ester group, a carboxyl group, a halogenated hydrocarbon group, or a halogen atom.
  • the color change of silver is mainly caused by sulfurization, and the cause of the color change is the formation of Ag 2 S.
  • the route through which the silver sulfidation reaction occurs is complex and not all is clear, but the overall reaction can be expressed as follows. 2Ag + S ⁇ Ag 2 S
  • the present inventors have found that the work function of silver is increased by using the compound represented by the above formula (I) together with silver nanoparticles. Although the detailed mechanism is unknown, it is thought as follows.
  • the structure (thiol group or carboxyl group) represented by Z of the compound is adsorbed on the surface of the silver nanoparticles and represented by R 1.
  • the electron-withdrawing structure specifically, an aromatic group or hydrocarbon group having an electron-withdrawing group, or a substituted or unsubstituted nitrogen-containing heterocyclic ring having an electron-withdrawing group
  • a dipole moment is generated from the electron-withdrawing structure toward the silver nanoparticle surface.
  • the silver nanoparticles try to emit electrons in this state, the emitted electrons must do extra work to overcome the dipole moment on the surface of the silver nanoparticles, so the work function of the silver nanoparticles will increase. It is done. As a result, it is considered that the sulfurization reaction of the silver nanoparticles is suppressed, and discoloration hardly occurs.
  • the decrease in silver glitter that may occur when the compound represented by the formula (I) is used as a silver discoloration inhibitor may be suppressed by using an emulsion resin as a binder resin.
  • an anti-color-change agent when used alone, when the image formed with ink is dried, the anti-color-change agent is deposited on the surface of the image during the drying process, and the smoothness of the image is lowered and the glitter is lowered. It is known.
  • the polarity is different from that of the anti-discoloring agent, so the compatibility is poor and the anti-discoloring agent is deposited on the surface of the image during the drying process, resulting in a decrease in image smoothness and glitter. Decreases.
  • the emulsion resin when used together with the anti-discoloring agent, the emulsion resin has a hydrophobic site, so the polarity with the anti-discoloring agent becomes close, so the precipitation of the anti-discoloring agent is suppressed and the image smoothness is suppressed. By preventing the decrease in brightness, it is considered that the decrease in brightness is suppressed.
  • the emulsion resin can enhance the adhesion between the image and the substrate, and can also improve the water resistance of the image.
  • Ink for forming the metallic luster layer of the present invention contains silver nanoparticles, a polymer dispersant adsorbed on the surface of the silver nanoparticles, a discoloration inhibitor, an emulsion resin, and water. .
  • Silver nanoparticles are nano-sized metal particles mainly composed of silver.
  • the silver nanoparticles may be mainly composed of silver alone, a silver alloy or a mixture.
  • the alloy containing silver include silver tin, silver zinc, silver copper, silver bismuth, silver palladium, silver palladium copper, and silver indium.
  • the silver nanoparticles may contain a small amount of other components inevitably contained, and may be surface-treated with citric acid or the like in order to improve dispersion stability. Moreover, you may contain the oxide of silver.
  • two or more kinds of silver nanoparticles having different types or compositions may be used in combination.
  • the average particle diameter of the silver nanoparticles is not particularly limited, but is preferably 3 nm or more and 100 nm or less, and more preferably 15 nm or more and 50 nm or less from the viewpoint of improving dispersion stability and storage stability in the ink. . If the particle size of the silver nanoparticles is less than 3 nm, the volume fraction of the dispersant is relatively increased in the metallic luster layer formed by applying the ink to the surface of the substrate, and the volume fraction of silver is lowered. Therefore, it is not desirable from the viewpoint of glitter. Furthermore, a particle size of 100 nm or more is not desirable because it is about half the wavelength of light and causes diffuse reflection of light.
  • the average particle diameter of silver nanoparticles can be made into the volume average particle diameter calculated
  • silver nanoparticle dispersion liquid containing silver nanoparticles and a polymer dispersant may be used.
  • commercially available silver nanoparticle dispersions include AGSK-5000W and AGSK-3000E (both particle content: 30%) manufactured by Shinko Chemical Industry Co., Ltd., and Silver nanoparticulate ink (30 wt% dispersion ink manufactured by Sigma-Aldrich).
  • Ethylene glycol Ethylene glycol
  • the content of the silver nanoparticles contained in the ink is not particularly limited, but is preferably 1% by mass or more and 35% by mass or less, and more preferably 5% by mass or more and 20% by mass or less with respect to the total mass of the ink. Preferably, it is 5 mass% or more and 13 mass% or less.
  • the polymer dispersant is a resin having an adsorption group for adsorbing on the surface of silver nanoparticles.
  • the adsorbing group include a carboxyl group and a thiol group. That is, in the present invention, whether the dispersant is adsorbed on the surface of the silver nanoparticles is determined by whether the dispersant has an adsorbing group and the silver nanoparticles are less aggregated and are well dispersed. be able to.
  • the polymer dispersant preferably has a molecular weight of 1,000 to 100,000, more preferably 2,000 to 50,000.
  • Examples of commercially available polymer dispersants that prevent the precipitation and aggregation of silver nanoparticles include Solsperse 24000, Solsperse 24000GR, Solsperse 32000 (all manufactured by Avecia, “Solsperse” is a registered trademark of the company), Addispar PB822, Addispar PB821, Azisper PB711 (both manufactured by Ajinomoto Fine Techno Co., Ltd., “Asper” is a registered trademark of the company), Disperbyk 160, Disperbyk 161, Disperbyk 162, Disperbyk 163, Disperbyk16 164, Disperbyk16 164, Disperbyk16 Disperbyk 2000, Disperbyk 001, Disperbyk 2015, Disperbyk 2050, Disperbyk 2150 (all manufactured by BYK Chemie, “Disperbyk” is a registered trademark of the company), Disparon ED-152, Disparon ED-211, Disparon ED-213, Disparon ED-213
  • the content of the polymer dispersant is not particularly limited, but from the viewpoint of sufficiently improving the adhesion of the silver nanoparticles to the substrate, it is 1% by mass to 15% by mass with respect to the total mass of the silver nanoparticles. Preferably, it is 2 mass% or more and 10 mass% or less, More preferably, it is 3 mass% or more and 8 mass% or less.
  • Discoloration inhibitor The compound used as a discoloration inhibitor is a compound represented by the following formula (I). (Where Z represents a thiol group or a carboxyl group, n is 1 or 2, R 1 represents an aromatic ring substituted with an electron-withdrawing group, a non-aromatic linear, branched or cyclic hydrocarbon group, or an electron-withdrawing substituted or unsubstituted nitrogen-containing heterocyclic ring. Represent, The electron withdrawing group is at least one of a nitro group, a cyano group, an amide group, an ester group, a carboxyl group, and a halogenated hydrocarbon group. )
  • Z in the formula (I) is an adsorbing group adsorbed on the surface of the silver nanoparticles, and is a thiol group or a carboxyl group.
  • R 1 in the formula (I) is a structure having an electron withdrawing property for capturing the electrons emitted from the silver nanoparticles and retaining them in the silver nanoparticles.
  • an aromatic ring or a non-aromatic linear, branched or cyclic hydrocarbon group substituted with an electron withdrawing group, or an electron withdrawing substituted or unsubstituted nitrogen-containing heterocyclic ring. is there.
  • non-aromatic linear, branched or cyclic hydrocarbon group used as R 1 , and even saturated hydrocarbons such as alkyl groups and cycloalkyl groups, and unsaturated hydrocarbons such as alkenyl groups and alkynyl groups. But you can. Although there is no limitation in particular in carbon number of these hydrocarbons, 1 or more and 20 or less are preferable and 6 or more and 18 or less are more preferable.
  • Examples of the electron withdrawing group for substituting the aromatic group or non-aromatic hydrocarbon group used as R 1 include a nitro group, a cyano group, an amide group, an ester group, a carboxyl group, and a halogenated hydrocarbon group (for example, fluorine Alkyl group substituted with an atom).
  • a halogenated hydrocarbon group for example, fluorine Alkyl group substituted with an atom.
  • the nitrogen-containing heterocyclic ring used as R 1 is not particularly limited, and may be substituted or unsubstituted, but it must be electron withdrawing.
  • the unsubstituted nitrogen-containing heterocycle include 5-membered rings such as pyrrole group, imidazole group and tetrazole group, 6-membered rings such as pyridine group, pyrimidine group and triazine group, indole ring, quinoline ring, isoquinoline ring and purine.
  • Examples thereof include a bicyclic structure such as a ring and a benzimidazole ring, a thiazole group containing a nitrogen atom and another element, a benzothiazole group, and the like.
  • the substituent that may substitute the nitrogen-containing heterocycle is not particularly limited, but the substituted nitrogen-containing heterocycle must be electron withdrawing.
  • substituents include nitro groups, cyano groups, amide groups, ester groups, carboxyl groups, optionally substituted alkyl groups, cycloalkyl groups, alkenyl groups (eg, vinyl groups), alkynyl groups, aromatic hydrocarbons. Groups (for example, phenyl groups), halogenated hydrocarbon groups (for example, alkyl groups substituted with fluorine atoms, aryl groups substituted with fluorine atoms), halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.) ) And the like.
  • a compound containing a triazine structure as R 1 is particularly preferable from the viewpoint of maintaining its resistance to sulfidation, that is, high discoloration prevention ability and the glitter of silver nanoparticles. .
  • the compound represented by the formula (I) include, but are not limited to, the following compounds. 6- (4-vinylbenzyl-n-propyl) amino-1,3,5-triazine-2,4-dithiol, 6- (N, Ndibutyl) amino-1,3,5-triazine-2,4- Dithiol, 2-mercaptobenzothiazole, 2-mercapto-5-nitrobenzimidazole, 5-mercapto-1-phenyl-1H-tetrazole, 2-mercaptopyrimidine, 4-mercaptobenzoic acid, 2,3,5,6-tetra Fluoro-4-mercaptobenzoic acid, pentafluorobenzenethiol, 2,3,5,6-tetrafluorobenzenethiol, 4-trifluoromethylbenzenethiol, 3-trifluoromethylbenzenethiol, 2-trifluoromethylbenzenethiol, 4-fluorobenzenethiol, 3-fluorobenzene
  • the content of the discoloration inhibitor is not particularly limited, but is preferably 1% by mass or more and 15% by mass or less, and more preferably 2% by mass or more and 10% by mass or less with respect to the total mass of the silver nanoparticles. Preferably, it is 3 mass% or more and 8 mass% or less. If it is 1% by mass or more, discoloration of the silver nanoparticles can be sufficiently prevented, and if it is 15% by mass or less, the glittering properties of the silver nanoparticles are not insufficient.
  • Emulsion resin The ink contains an emulsion resin as a binder resin.
  • the emulsion resin interacts with the polymer dispersant adsorbed on the surface of the silver nanoparticles to enhance the adhesion of the silver nanoparticles to the substrate, and further, due to the anti-discoloring agent adsorbed on the surface of the silver nanoparticles. Decrease in glitter can be suppressed.
  • Emulsion resin is an aqueous dispersion of resin particles. Therefore, as resin components constituting the resin particles contained in the emulsion resin, hydrophobic resins such as acrylic resins, urethane resins, ester resins, vinyl acetate resins, styrene-butadiene resins, vinyl chloride resins Acryl-styrene resin, butadiene resin, styrene resin and the like. Among these, from the viewpoint of water resistance, acrylic resins, urethane resins, and polyester resins are preferable, and acrylic resins and urethane resins are particularly preferable.
  • the emulsion resin can be obtained by dispersing resin particles in water.
  • the monomer used as the raw material of resin can also be polymerized in an aqueous medium by a well-known emulsion polymerization method, and the aqueous dispersion (namely, emulsion) of a resin particle can also be obtained directly.
  • an acrylic resin emulsion can be obtained by polymerizing (meth) acrylic acid ester in water in the presence of a polymerization initiator.
  • An emulsion of urethane resin can be obtained by emulsion polymerization of polyester polyol and diisocyanate in water.
  • the emulsion resin may be a commercially available water-dispersed resin.
  • commercially available water-dispersed resins that can be used for ink production include Kanebinol KD27 and iodosol AD57, which are acrylic resin aqueous dispersions manufactured by Henkel, and Vylonal MD1200, MD1245, and MD2000, which are polyester resin aqueous dispersions manufactured by Toyobo.
  • Examples thereof include Superflex 650, which is a polyurethane resin aqueous dispersion manufactured by Daiichi Kogyo Seiyaku Co., Ltd., SE841E and SE1658 manufactured by Taisei Fine.
  • the average particle size of the resin particles contained in the emulsion is preferably 10 nm to 200 nm, more preferably 30 nm to 100 nm.
  • the average particle diameter of the resin particles can be a volume average particle diameter determined using a particle size distribution measuring apparatus based on a dynamic light scattering method.
  • the solid content of the resin emulsion in the ink is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 0.5% by mass or more and 2% by mass or less with respect to the total mass of the ink. .
  • Dispersion medium The ink contains water as a dispersion medium.
  • the dispersion medium is preferably water from the viewpoint of safety to the human body and ease of processing, but a known organic solvent may optionally be included together with water for viscosity adjustment and the like.
  • the organic solvent that the ink may contain include the following organic solvents.
  • the glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether (DEGEE), diethylene glycol monobutyl ether (DEBE), triethylene glycol monomethyl ether, triethylene glycol monomethyl ether.
  • Ethyl ether triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether (tetra EGME), tetraethylene glycol monoethyl ether (tetra EGEE), tetraethylene glycol monopropyl ether (tetra EGPE), tetraethylene glycol monobutyl ether (tetra EGBE) , B propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether (DPGME), dipropylene glycol monoethyl ether (DPGEE), dipropylene glycol monopropyl ether (DPGPE), Polyhydric alcohols include ethylene glycol, glycerin, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, tetraethylene glycol, triethylene glycol, tripropylene glycol, 1,2,4-but
  • the organic solvent is contained in the ink, it is preferably 20% by mass or more and 50% by mass or less, and more preferably 30% by mass or more and 45% by mass or less with respect to the total mass of the ink.
  • a stabilizer may be added for the purpose of stably dissolving.
  • a compound that converts the discoloration inhibitor into a water-soluble salt can be used. Specific examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, lithium acetate, monoethanolamine, dimethylaminoethanol, diethanolamine, triethanolamine, trishydroxymethylaminomethane, Polyethyleneimine etc. are mentioned. From the viewpoint of enhancing the glitter of the image formed with the ink, amines such as monoethanolamine, diethanolamine, and triethanolamine are particularly preferable. These may be used alone or in combination.
  • the stabilizer When the stabilizer is contained in the ink, it is preferably 0.01% by mass or more and 6% by mass or less, and 0.05% by mass or more and 3% by mass or less with respect to the total mass of the ink. Is more preferable. If the content of the stabilizer is 0.05% by mass or more, the anti-discoloring agent can be stably dissolved in the ink, and as a result, the brightness of the image formed by the ink may be improved. is there. Moreover, if it is 3 mass% or less, the film
  • the ink may contain a known surfactant (surface conditioner).
  • surfactants include anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates and fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols and polyoxy Nonionic surfactants such as ethylene / polyoxypropylene block copolymers, cationic surfactants such as alkylamine salts and quaternary ammonium salts, and silicone-based and fluorine-based surfactants are included.
  • silicone surfactants examples include KF-351A, KF-352A, KF-642 and X-22-4272, manufactured by Shin-Etsu Chemical, BYK307, BYK345, BYK347 and BYK348, manufactured by Big Chemie (“BYK "Is a registered trademark of the same company), as well as TSF4452, manufactured by Toshiba Silicone.
  • the content of the surfactant can be, for example, 0.001% by mass or more and less than 1.0% by mass with respect to the total mass of the ink.
  • the ink is composed of silver nanoparticles substantially adsorbed by the polymer dispersant and the anti-discoloration agent, the emulsion resin and the dispersion medium, and It is preferably composed of a necessary amount of a surfactant.
  • the total content of the silver nanoparticles adsorbed by the polymer dispersant and the discoloration inhibitor, the emulsion resin and the dispersion medium is preferably 90% by mass or more and 100% by mass or less with respect to the total mass of the ink. More preferably, the content is 95% by mass or more and 100% by mass or less.
  • Ink Preparation Method There is no particular limitation on the ink preparation method, but silver nanoparticles, a polymer dispersant adsorbed on the surface of the silver nanoparticles, a discoloration inhibitor, an emulsion resin, water, and other desired ones Ink can be obtained by mixing with the above components and then filtering with a membrane filter or the like.
  • the content of solid content in the emulsion resin is usually 1% by mass to 50% by mass, and preferably 20% by mass to 30% by mass.
  • the solid content of the emulsion resin can be adjusted by dilution with water or dehydration by filtration or the like.
  • the viscosity of the ink is preferably 1 cP or more and less than 100 cP from the viewpoint of further improving the ejection stability from the nozzle. More preferably, it is more preferably 1 cP or more and 15 cP or less.
  • the image forming method of the present invention includes a step of forming the metallic gloss layer by applying the above-described ink of the present invention to the surface of the substrate.
  • the substrate for applying the ink is not particularly limited, and an absorbent substrate including art paper, coated paper, lightweight coated paper, coated paper including fine coated paper and cast paper, and non-coated paper.
  • Material paper substrate
  • polyester PET
  • polyvinyl chloride PVC
  • PE polyethylene
  • PU polyurethane
  • PP polypropylene
  • PA acrylic resin
  • PC polycarbonate
  • PS polystyrene
  • Non-absorbent substrates plastic substrates composed of plastics including acrylonitrile-butadiene-styrene copolymer (ABS), polyethylene terephthalate (PET) and polybutadiene terephthalate (PBT), and metals and glass
  • a non-absorbing inorganic medium can be used.
  • the method for applying the ink to the surface of the base material is not particularly limited, and the ink may be applied to the surface of the base material using a roll coater or a spin coater, or spray coating, dipping method, screen printing, gravure.
  • the ink may be applied to the surface of the substrate by a method such as printing or offset printing, or the ink may be landed on the surface of the substrate by an inkjet method.
  • the inkjet method is preferable from the viewpoint of forming a finer recorded matter.
  • an inkjet ink containing silver nanoparticles, emulsion resin and water adsorbed with the above-described polymer dispersant and anti-discoloration agent can be ejected from the nozzle of the inkjet head and landed on the surface of the substrate. That's fine.
  • the ink may be dried after the ink is applied.
  • the drying temperature at this time is preferably less than 100 ° C, and more preferably less than 80 ° C.
  • Image-formed product of the present invention is formed by applying the above-described ink of the present invention to the surface of a base material, silver nanoparticles contained in the ink of the present invention, a polymer dispersant, Contains a discoloration inhibitor and an emulsion resin.
  • the metallic luster layer is a layer containing silver nanoparticles.
  • the metallic luster layer includes silver nanoparticles and a binder resin on which a polymer dispersant and a discoloration preventing agent are adsorbed.
  • the metallic luster layer is composed of silver nanoparticles and binder resin (that is, resin components in the emulsion resin) in which the polymer dispersant and the anti-discoloring agent are substantially adsorbed.
  • binder resin that is, resin components in the emulsion resin
  • the polymer dispersant and the anti-discoloring agent are substantially adsorbed.
  • the total content of the silver nanoparticles adsorbed by the polymer dispersant and the discoloration inhibitor and the binder resin is preferably 90% by mass or more and 100% by mass or less with respect to the total mass of the metallic luster layer. More preferably, it is at least 100% by mass.
  • the thickness of the metallic luster layer is not particularly limited, but from the viewpoint of sufficiently expressing the metallic luster, it is preferably 0.005 ⁇ m or more and 10 ⁇ m or less, more preferably 0.01 ⁇ m or more and 1.0 ⁇ m or less, More preferably, it is 0.1 ⁇ m or more and 0.5 ⁇ m or less.
  • a metallic luster layer does not contain substantially the compound which can be fluctuate
  • the image formed product may include layers other than the above-described metallic gloss layer.
  • the image-formed product may have a primer layer for further improving the adhesion of silver nanoparticles on the base material side of the metallic gloss layer, or more on the surface layer side (opposite side of the base material).
  • You may have a color material layer or a protective layer.
  • the primer layer can be a layer formed from a material conventionally used to enhance adhesion to a substrate such as a pigment containing silver nanoparticles.
  • the primer layer includes a fixing resin.
  • the film thickness of the primer layer is not particularly limited, but from the viewpoint of sufficiently improving the adhesion of the metallic luster layer to the substrate, it is preferably 0.05 ⁇ m or more and 100 ⁇ m or less, and is 0.1 ⁇ m or more and 50 ⁇ m or less. Is more preferably 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the fixing resin may be any resin that has been conventionally used to enhance the adhesion of a pigment containing silver nanoparticles or the like to the base material, and may be the same resin as the binder resin described above. .
  • the fixing resin examples include (meth) acrylic resin, epoxy resin, polysiloxane resin, maleic acid resin, polyolefin resin, vinyl resin, polyamide resin, polyvinyl pyrrolidone, polyhydroxystyrene, polyvinyl alcohol, nitrocellulose, acetic acid Examples include cellulose, ethyl cellulose, ethylene-vinyl acetate copolymer, urethane resin, polyester resin, and alkyd resin. These fixing resins may be used alone or in combination of two or more.
  • the amount of the fixing resin applied to the substrate surface is preferably 0.01 g / m 2 or more and 100 g / m 2 or less from the viewpoint of sufficiently improving the adhesion of the metallic gloss layer to the substrate, more preferably 0.05 g / m 2 or more 50 g / m 2 or less, and further preferably 0.1 g / m 2 or more and 10 g / m 2 or less.
  • the color material layer is a layer for changing the color tone of the image formed product to express a specific metallic color.
  • the color material layer may be a layer containing a known pigment or dye and a resin for fixing the pigment or dye.
  • the resin for fixing the pigment or dye can be selected from the same resin as the binder resin included in the ink (that is, the resin component in the emulsion resin) and the fixing resin included in the primer layer.
  • the said color material layer may contain these resin individually by 1 type, and may contain it in combination of 2 or more types.
  • the protective layer is a layer that enhances the scratch resistance of the metallic gloss layer and suppresses the release of silver nanoparticles from the image-formed product.
  • the protective layer may be a layer containing the same resin as the binder resin contained in the ink (that is, the resin component in the emulsion resin) and the fixing resin contained in the primer layer.
  • the said protective layer may contain these resin individually by 1 type, and may contain it in combination of 2 or more types.
  • the image formed product can be preferably used for applications requiring the expression of metallic luster.
  • the image formed material can be used as a recorded material.
  • the recorded matter may be a single character or a set of characters, or may be an image such as a figure, a picture, or a photograph.
  • Material 1-1 Silver nanoparticles The following commercially available silver nanoparticle dispersions were used as silver nanoparticles. AGSK-5000W: manufactured by Shinko Chemical Industry Co., Ltd., AGSK-3000E (particle content: 30%)
  • Resin As the emulsion resin, the following commercially available emulsion resin diluted with water to a solid content of 20% by mass was used.
  • KD27 manufactured by Henkel
  • Kanebinol KD27 acrylic resin aqueous dispersion
  • MD1200 manufactured by Toyobo
  • Vylonal MD1200 polyyester resin aqueous dispersion
  • SF650 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • Superflex 650 polyurethane resin aqueous dispersion
  • polyacrylic acid molecular weight: 5000
  • diluted with water and prepared to a solid content of 20% by mass was used.
  • Anti-discoloring agent The following compounds were used as anti-discoloring agents, and a 1.2% by mass solution using ⁇ -butyrolactone as a solvent was prepared and used. 6- (N, N-dibutylamino) -1,3,5-triazine-2,3-dithiol 6- (4-vinylbenzyl-n-propylamino) -1,3,5-triazine-2,4- Dithiol 2-mercaptobenzothiazole
  • Stabilizers The following compounds were used as stabilizers for discoloration inhibitors. N, N-dimethylaminoethanol
  • Example 1 50 parts by mass of AGSK-5000W, 42 parts by mass of ⁇ -butyrolactone solution of 6- (N, N-dibutylamino) -1,3,5-triazine-2,3-dithiol, and 8 parts by mass of KD27 are mixed. Then, the mixture was filtered through a 3 ⁇ m membrane filter manufactured by ADVATEC (Teflon is a registered trademark of DuPont) to obtain ink 1.
  • ADVATEC AdVATEC
  • Examples 2 to 9, Comparative Examples 1 to 11 The above components were mixed according to the composition described in Table 1 below, and then filtered through a 3 ⁇ m membrane filter manufactured by ADVATEC (“Teflon” is a registered trademark of DuPont) to obtain inks 2 to 20.
  • AdVATEC AdVATEC
  • an ink was prepared using the same part by mass of water when no resin was used, and using the same part by mass of ⁇ -butyrolactone when no discoloration inhibitor was used.
  • the ink jet recording apparatus includes an ink tank, an ink supply pipe, an ink supply tank immediately before the ink jet head, a filter, and a piezo type ink jet head (evaluation printer head KM512L (discharge amount 42 pl)) from the upstream side where the ink flows. We had in this order toward the downstream side.
  • the inkjet head is driven under the conditions of a droplet amount of 14 pl, a printing speed of 0.5 m / sec, an ejection frequency of 10.5 kHz, and a printing rate of 100%, and droplets of ink 1 to ink 20 are applied to each of the substrates. Ejected and landed. After landing, it was heated and dried at 120 ° C. for 5 minutes to obtain image-formed product 1 to image-formed product 20.
  • Evaluation Image formation 1 to image formation 20 were evaluated according to the following criteria.
  • a petri dish containing sulfur powder was placed in a sealable glass bottle. Subsequently, the image formed product was placed at a position 10 cm away from the petri dish containing sulfur powder, and the container was sealed. The container was heated at 80 ° C. for 7 hours, and the image formed product was exposed to a sulfur vapor atmosphere. Thereafter, the image formed product was taken out from the glass bottle, and the change in reflectance in the visible light region was measured.
  • ⁇ E * ab [( ⁇ L *) 2+ ( ⁇ a *) 2+ ( ⁇ b *) 2] 1/2 ⁇ : ⁇ E * ab is less than 5 ⁇ : ⁇ E * ab is 5 or more and less than 25 ⁇ : ⁇ E * ab is 25 or more and less than 50 ⁇ : ⁇ E * ab is 50 or more
  • Scratch resistance Film strength was evaluated according to the 6.2.3 rub resistance test in JIS K5701-1. Specifically, a coated paper for printing (OK top coat, basis weight 128 g / m 2 , manufactured by Oji Paper Co., Ltd.) cut to an appropriate size was placed on the image formed product and rubbed under a load. . Thereafter, the degree of reduction in image density was visually observed, and scratch resistance was evaluated according to the following criteria. ⁇ : No change is observed even after rubbing 30 times or more. ⁇ : Change is observed at the stage of rubbing 30 times, but is practically acceptable. X: An obvious change is observed with rubbing less than 30 times. The quality is unbearable
  • the inks of Examples 1 to 9 are inks containing both emulsion resin and anti-discoloring agent together with silver nanoparticles. Image formations 1 to 9 produced using these inks all have sufficient brightness for practical use and excellent sulfidation resistance, so that discoloration is prevented. It was excellent in scratch resistance, adhesion and water resistance.
  • Examples 1 to 6 in which the discoloration inhibitor is a compound containing a triazine structure have better results than Examples 7 to 9 in which the discoloration inhibitor is a compound not containing a triazine structure. It was.
  • the inks 1 to 6 of Examples 1 to 6 were higher in glitter and sulfidation resistance than the inks 7 to 9 of Examples 7 to 9.
  • Examples 1 and 4 using KD27 which is an acrylic resin as an emulsion resin, and Examples 3 and 6 using SF650 which is a urethane resin were very excellent in water resistance.
  • the inks 4 to 6 of Examples 4 to 6 containing N, N-dimethylaminoethanol as a stabilizer have higher glossiness than the inks 1 to 3 of Examples 1 to 3 not containing the stabilizer. It was. This is presumably because the discoloration inhibitor was stably dissolved in a mixed solvent of water and an organic solvent by using the stabilizer.
  • the image-formed product 10 produced using the ink of Comparative Example 1 containing silver nanoparticles but containing neither an emulsion resin nor a discoloration inhibitor showed high glitter, but was poor in sulfur resistance and discolored. Furthermore, the scratch resistance, adhesion, and water resistance were also poor.
  • the image formations 11 to 13 produced using the inks of Comparative Examples 2 to 4 which contain silver nanoparticles and a color change inhibitor and do not contain an emulsion resin were excellent in sulfidation resistance. Scratch resistance and adhesion, and water resistance were poor.
  • the image formed products 14 to 16 produced using the inks of Comparative Examples 5 to 7 which contain silver nanoparticles and an emulsion resin and do not contain an anti-discoloring agent have scratch resistance and adhesion, and Although the water resistance was excellent, the sulfidation resistance was poor.
  • the image products 17 to 20 produced using the inks of Comparative Examples 8 to 11 using a water-soluble resin instead of the emulsion resin were excellent in scratch resistance and adhesion, they were poor in sulfidation resistance and water resistance. Sex was inferior.
  • the ink of the present invention can prevent discoloration while maintaining the glitter of silver, and can improve image adhesion and water resistance. Therefore, the present invention is expected to expand the range of application of glittering recorded materials and contribute to the advancement and spread of technology in the same field.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

L'objectif de la présente invention est de fournir une encre qui contient des nanoparticules d'argent, ladite encre étant apte à empêcher la décoloration de l'argent et à améliorer l'adhérence et la résistance à l'eau d'une image tout en conservant la photoluminescence de l'argent. Cette encre est destinée à former une couche de lustre métallique, ladite encre contenant des nanoparticules d'argent, un dispersant polymère, l'agent de prévention de décoloration représenté par la formule (I), une résine d'émulsion et de l'eau. (Dans la formule, Z représente un groupe thiol ou un groupe carboxyle, n vaut 1 ou 2, R1 représente : un cycle aromatique substitué par un groupe attracteur d'électrons ; un groupe hydrocarboné non aromatique, linéaire, ramifié ou cyclique ; ou un hétérocycle contenant de l'azote substitué ou non substitué attracteur d'électrons, et le groupe attracteur d'électrons est au moins un groupe parmi un groupe nitro, un groupe cyano, un groupe amide, un groupe ester, un groupe carboxyle et un groupe hydrocarboné halogéné)
PCT/JP2018/014699 2017-04-25 2018-04-06 Encre, procédé de formation d'image, objet formé par image WO2018198722A1 (fr)

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JP2003049091A (ja) * 2001-08-03 2003-02-21 Toyo Aluminium Kk メタリック顔料組成物、塗料組成物、インキ組成物、樹脂組成物、ゴム組成物およびメタリック顔料組成物の製造方法
JP2005120226A (ja) * 2003-10-16 2005-05-12 General Kk インク組成物
WO2006112031A1 (fr) * 2005-04-14 2006-10-26 General Technology Company Limited Composition d’encre et procede d’impression utilisant celle-ci.
JP2008297323A (ja) * 2007-05-29 2008-12-11 Mitsuboshi Belting Ltd 無機光沢性インキ組成物及び筆記具
JP2009269935A (ja) * 2008-04-30 2009-11-19 Sumitomo Metal Mining Co Ltd 金色系金属光沢を有する銀膜
JP2011140635A (ja) * 2009-12-10 2011-07-21 Riso Kagaku Corp 導電性エマルジョンインク及びそれを用いた導電性薄膜の形成方法
JP2012041378A (ja) * 2010-08-12 2012-03-01 Seiko Epson Corp インク組成物および印刷物
JP2012101491A (ja) * 2010-11-11 2012-05-31 Seiko Epson Corp インクジェット記録方法及び記録物
JP2014214986A (ja) * 2013-04-26 2014-11-17 コニカミノルタ株式会社 太陽熱発電用ミラー及びそれを具備した太陽熱発電用反射装置

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JP2007073267A (ja) * 2005-09-05 2007-03-22 Alps Electric Co Ltd 導電膜及びその製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003049091A (ja) * 2001-08-03 2003-02-21 Toyo Aluminium Kk メタリック顔料組成物、塗料組成物、インキ組成物、樹脂組成物、ゴム組成物およびメタリック顔料組成物の製造方法
JP2005120226A (ja) * 2003-10-16 2005-05-12 General Kk インク組成物
WO2006112031A1 (fr) * 2005-04-14 2006-10-26 General Technology Company Limited Composition d’encre et procede d’impression utilisant celle-ci.
JP2008297323A (ja) * 2007-05-29 2008-12-11 Mitsuboshi Belting Ltd 無機光沢性インキ組成物及び筆記具
JP2009269935A (ja) * 2008-04-30 2009-11-19 Sumitomo Metal Mining Co Ltd 金色系金属光沢を有する銀膜
JP2011140635A (ja) * 2009-12-10 2011-07-21 Riso Kagaku Corp 導電性エマルジョンインク及びそれを用いた導電性薄膜の形成方法
JP2012041378A (ja) * 2010-08-12 2012-03-01 Seiko Epson Corp インク組成物および印刷物
JP2012101491A (ja) * 2010-11-11 2012-05-31 Seiko Epson Corp インクジェット記録方法及び記録物
JP2014214986A (ja) * 2013-04-26 2014-11-17 コニカミノルタ株式会社 太陽熱発電用ミラー及びそれを具備した太陽熱発電用反射装置

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