WO2013179838A1 - Jeu d'encres aqueuses pour enregistrement par jet d'encre - Google Patents

Jeu d'encres aqueuses pour enregistrement par jet d'encre Download PDF

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Publication number
WO2013179838A1
WO2013179838A1 PCT/JP2013/062449 JP2013062449W WO2013179838A1 WO 2013179838 A1 WO2013179838 A1 WO 2013179838A1 JP 2013062449 W JP2013062449 W JP 2013062449W WO 2013179838 A1 WO2013179838 A1 WO 2013179838A1
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Prior art keywords
ink
resin
polymer
group
water
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PCT/JP2013/062449
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English (en)
Japanese (ja)
Inventor
木村　利久
雪彦 川原田
佐藤　義浩
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Dic株式会社
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Priority to JP2013540126A priority Critical patent/JP5500410B1/ja
Publication of WO2013179838A1 publication Critical patent/WO2013179838A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing

Definitions

  • the present invention relates to a water-based ink set for inkjet recording.
  • Printing with an inkjet printer recording device is a method that ejects ink from nozzles and adheres to the recording material. Unlike conventional printing methods, this is a printing method that does not use a plate, so on-demand printing that can accommodate a small variety of products This printing method is expected to be used in a wide range of fields.
  • a recording material there have been many studies on printing on a non-absorbing substrate such as plastic from printing on a conventional absorbing substrate such as paper, and printing using pigment inks from the viewpoint of weather resistance, among others. Is being studied.
  • a receiving layer is provided on a plastic film (for example, refer to Patent Document 1).
  • the surface of the plastic film has poor adhesion to the ink-jet ink, and a layer usually called an anchor layer, primer layer, undercoat layer, adhesive layer, etc. is formed on the film surface, and polyurethane, polyacryl, etc.
  • the step of providing an ink receiving layer containing as a main component was essential. Such a surface treatment process not only leads to an increase in cost, but also requires a lot of time for production because the number of processes increases.
  • a printing method of an aqueous inkjet recording method that is excellent in image quality and abrasion resistance and excellent in discharge stability regardless of ink absorption of the recording medium with respect to a non-absorbing substrate such as plastic, color ink, resin
  • a printing method for printing an image by applying ink and reactive ink is known (see, for example, Patent Document 2).
  • a color ink containing a water-insoluble colorant, a water-soluble and / or water-insoluble resin component, a water-soluble solvent, and a surfactant, a water-soluble resin solvent, and water-soluble but not soluble in water.
  • the resin resin solvent contains thermoplastic resin particles that are compatible, and the total content of the resin particles is greater than or equal to the content of the colorant contained in the color ink; a polyvalent metal salt; Three inks of a reactive agent selected from allylamine and its derivatives and a reactive ink containing a surfactant are applied to form an image.
  • this method must prepare at least three kinds of inks, and requires an ink jet apparatus having a high degree of ejection accuracy.
  • a step of applying a liquid composition containing a cationic substance and an ink containing an anionic substance to a recording medium so as to contact each other on the recording medium There is known a method of eliminating image disturbance such as bleeding and intercolor bleeding by a printing method having a color (for example, see Patent Document 3).
  • Patent Document 3 a method of eliminating image disturbance such as bleeding and intercolor bleeding by a printing method having a color.
  • An object of the present invention is to provide a two-component water-based ink set for ink-jet recording that is excellent in abrasion resistance immediately after printing without causing image disturbance such as bleeding and intercolor bleeding even when printed on a plastic film. .
  • the present inventors have prepared a first pigment ink containing a resin having a hydroxy group and / or a carboxyl group, vinylpyrrolidone N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer ( B) and at least one polymer selected from the group consisting of a core-shell amphoteric emulsion polymer (C), a water-soluble solvent and / or a second ink containing water, and a two-component water-based ink set for inkjet recording
  • a resin having a hydroxy group and / or a carboxyl group vinylpyrrolidone N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer ( B) and at least one polymer selected from the group consisting of a core-shell amphoteric emulsion polymer (C), a water-soluble solvent and / or a
  • the present invention is an ink set for ink jet recording using at least two kinds of inks, and the first ink contains a color material, a resin having a hydroxy group and / or a carboxyl group, a water-soluble solvent and / or water.
  • the second ink is selected from the group consisting of vinylpyrrolidone N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), and core-shell amphoteric emulsion polymer (C).
  • An aqueous ink set for ink jet recording comprising at least one polymer, a water-soluble solvent and / or water is provided.
  • an aqueous ink set for ink-jet recording that gives a printed matter that is free from image disturbance such as bleeding and intercolor bleeding even when printed on a plastic film and has excellent abrasion resistance immediately after printing.
  • the first ink is an ink containing a color material, a resin having a hydroxy group and / or a carboxyl group, a water-soluble solvent and / or water
  • the second ink is a vinyl At least one polymer selected from the group consisting of pyrrolidone N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), and core-shell amphoteric emulsion polymer (C), a water-soluble solvent, and Ink containing water.
  • At least one polymer selected from the group consisting of vinylpyrrolidone N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), and core-shell amphoteric emulsion polymer (C) Contains a cationic group.
  • the polymer becomes a trigger and grows into a large aggregate by intermolecular hydrogen bonding of a resin having a hydroxy group and / or a carboxyl group, and is bundled into a network by interaction such as van der Waals force.
  • the first ink used in the present invention contains a color material, a resin having a hydroxy group and / or a carboxyl group, a water-soluble solvent and / or water.
  • the resin having a hydroxy group and / or a carboxyl group is not particularly limited as long as a conventionally known resin having a hydroxy group and / or a carboxyl group may be used.
  • the resin having a hydroxy group and / or a carboxyl group in the present invention may have a resin having at least a hydroxy group and / or a carboxyl group.
  • the acquisition form of the resin which has the said carboxyl group is not specifically limited.
  • a dispersion of a resin in a water-soluble solvent and / or water that is, a so-called resin emulsion is preferably used rather than a solid. Commercially available resin emulsions may also be used.
  • An emulsion is preferable, and a resin emulsion in which resin particles of a polyolefin resin are dispersed in a water-soluble solvent and / or water is more preferable.
  • the content (% by mass) of the resin having a hydroxy group and / or a carboxyl group in the first ink is 2.0% by mass or more and 15.0% by mass or less based on the total mass of the ink.
  • 3.0 mass% or more and 8.0 mass% or less are still more preferable, and 3.0 mass% or more and 5.0 mass% or less are still more preferable.
  • the acid value of the resin having a hydroxy group and / or a carboxyl group is preferably 10 to 200 mgKOH / g per resin solid content. If the acid value is less than 10 mgKOH / g, the storage stability of the ink may be inferior. On the other hand, when the acid value exceeds 200 mgKOH / g, physical properties such as preferable durability and water resistance may not be obtained.
  • the range is more preferably 5 to 100 mgKOH / g, still more preferably 10 to 80 mgKOH / g, and still more preferably 15 to 60 mgKOH / g.
  • the hydroxyl value of the resin having a hydroxy group and / or a carboxyl group is preferably 30 mgKOH / g or less per resin solid content. If the hydroxyl value exceeds 30 mgKOH / g, the storage stability of the ink may be inferior. More preferably, it is 20 mgKOH / g or less, More preferably, it is 10 mgKOH / g or less.
  • the acid value and hydroxyl value here are the values measured by the method based on JIS0070.
  • the glass transition temperature (hereinafter abbreviated as Tg) of the resin having a hydroxy group and / or a carboxyl group is preferably set as appropriate according to the desired application.
  • Tg glass transition temperature
  • the Tg of the resin having a hydroxy group and / or carboxyl group is preferably in the range of ⁇ 80 ° C. to 80 ° C., and ⁇ 80 ° C. to A range of 30 ° C. is particularly preferable.
  • the resin having a hydroxy group and / or carboxyl group has a weight average molecular weight (polystyrene conversion) of 10,000 or more and 1,000,000 or less, more preferably 20,000 or more and 700,000 or less. This is preferable because a physical property balance is easily developed.
  • the average particle size of the resin particles having a hydroxy group and / or a carboxyl group is as small as possible because the influence on ejection failure is small. Specifically, it is preferably in the range of 10 nm to 500 nm, particularly preferably in the range of 10 to 300 nm.
  • the particle diameter can be measured by a known and common centrifugal sedimentation method, laser diffraction method (light scattering method), ESA method, capillary method, electron microscope method, or the like. Preferable is measurement by Microtrac UPA using a dynamic light scattering method.
  • the resin emulsion that can be used in the ink of the present invention may contain an emulsifier without particular limitation within a range not impairing the effects of the present invention, depending on the desired physical properties.
  • an emulsifier without particular limitation within a range not impairing the effects of the present invention, depending on the desired physical properties.
  • it may be a resin emulsion obtained by a method of dropping a monomer and a polymerization initiator in the presence of an emulsifier and polymerizing, or an emulsification method by stirring an aqueous solution or suspension of a resin.
  • resin emulsions without addition of an emulsifier may be obtained by making full use of various emulsification / dispersion techniques such as an ultrasonic irradiation technique.
  • nonionic emulsifiers such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyoxyethylene alkyl ether carboxylates, dialkyl sulfosuccinates, water-soluble acrylic resins
  • Carboxylic acid types such as polycarboxylic acid salts, sulfonic acid types such as alkylbenzene sulfonates, anionic emulsifiers such as alcohol sulfate esters and alkylallyl sulfonates.
  • the polyolefin resin in the present invention has a polar group such as an amino group, a carboxyl group, and a hydroxyl group via a covalent bond to a hydrophobic polyolefin skeleton within a range that does not impair the effects of the present invention, depending on the desired physical properties, It can be set as the modified polyolefin which introduce
  • a method for producing a modified polyolefin that is, a method for introducing a polar group or a polymer chain via a covalent bond to a polyolefin skeleton, a method for polymerizing a monomer having a polar group in the presence of a polyolefin, or a method for polymerizing a polymer chain into a polyolefin.
  • the method include bonding.
  • the types and combinations of polyolefins, polar group-containing monomers and polymer chains can be appropriately selected.
  • the chemical structure classification of the modified polyolefin is not particularly limited, and may be any of a random copolymer, a block copolymer, a graft modified product, and the like.
  • the polyolefin any of a polyolefin having no reactive group or a polyolefin having a reactive group can be used.
  • polyolefin having no reactive group various known polyolefins and modified polyolefins can be used, and are not particularly limited.
  • ethylene or propylene homopolymer ethylene / propylene copolymer, ethylene or / And copolymers of propylene and other comonomers.
  • comonomers include ⁇ -olefin comonomers having 2 or more carbon atoms such as butene-1, pentene-1, hexene-1, heptene-1, octene-1, cyclopentene, cyclohexene, and norbornene.
  • the ⁇ -olefin comonomer is preferably an ⁇ -olefin comonomer having 2 to 8 carbon atoms, more preferably an ⁇ -olefin comonomer having 2 to 6 carbon atoms, and still more preferably an ⁇ -olefin comonomer having 2 to 4 carbon atoms. It is.
  • copolymers of these ⁇ -olefin comonomers can be used.
  • a hydrogenated product of a copolymer of an ⁇ -olefin monomer and a comonomer such as vinyl acetate, acrylic acid ester or methacrylic acid ester, or a copolymer of two or more monomers selected from an aromatic vinyl monomer and a conjugated diene monomer , Etc. can also be used.
  • a copolymer when only calling it a copolymer, it may be a random copolymer or a block copolymer.
  • the polyolefin may be linear or branched.
  • chlorinated polyolefins obtained by chlorinating these polyolefins can also be used.
  • the chlorination degree of the chlorinated polyolefin is usually 5% by weight or more, preferably 10% by weight or more, and the chlorination degree is usually 50% by weight or less, preferably 30% by weight or less.
  • substantially containing no chlorine means, for example, that the chlorination rate of polyolefin is less than 5% by weight.
  • Examples of the polyolefin having a reactive group include a copolymer obtained by copolymerizing an unsaturated compound having no reactive group and an unsaturated compound having a reactive group at the time of polyolefin polymerization, or radical polymerization having a reactive group.
  • a polymer obtained by graft-polymerizing a polymerizable unsaturated compound onto a polyolefin, or a polymer obtained by converting a polyolefin having an unsaturated end group into an element group of group 13 to group 17 can be used.
  • Examples of the reactive group include a carboxylic acid group, a dicarboxylic acid anhydride group, and a dicarboxylic acid anhydride monoester group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, and the like, and a carboxylic acid group and a dicarboxylic acid anhydride group. And a dicarboxylic anhydride monoester group is more preferred.
  • Carboxylic acid groups, dicarboxylic acid anhydride groups, and dicarboxylic acid anhydride monoester groups are not only highly reactive and easy to bond with hydrophilic polymers, but also contain many unsaturated compounds having these groups and are common to polyolefins. This is because polymerization or graft reaction is also easy, and so-called acid-modified polyolefin resins in which polyolefin has these groups are excellent in water dispersibility.
  • a copolymer obtained by copolymerizing an unsaturated compound having no reactive group at the time of polyolefin polymerization and an unsaturated compound having a reactive group is a copolymer in which an unsaturated compound having a reactive group is inserted into the main chain. It is.
  • ⁇ -olefin such as ethylene, propylene, butene, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, (meth) acrylic acid (dimethylamino) ) Ethyl, (meth) acrylic acid (2-isocyanato) ethyl, and ⁇ , ⁇ -unsaturated carboxylic acid such as maleic anhydride, the same ester or anhydride.
  • ⁇ -olefin such as ethylene, propylene, butene
  • acrylic acid 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, (meth) acrylic acid (dimethylamino) ) Ethyl, (meth) acrylic acid (2-isocyanato) ethyl
  • ⁇ -unsaturated carboxylic acid such as maleic
  • (meth) acrylic acid means “acrylic acid or methacrylic acid”).
  • specific examples of these copolymers include propylene-butene-maleic anhydride copolymers. These may be used individually by 1 type and may be used in combination of 2 or more type. Of course, it is also possible to use a commercially available product.
  • a polymer obtained by graft-polymerizing a radically polymerizable unsaturated compound having a reactive group to a polyolefin is obtained by graft-polymerizing a radically polymerizable unsaturated compound having a reactive group to a previously polymerized polyolefin.
  • the unsaturated compound it has is grafted to the main chain.
  • These may be used individually by 1 type and may be used in combination of 2 or more type.
  • polyolefin of this reaction the polyolefin which does not have the above-mentioned reactive group can be used.
  • Specific examples of the polymer obtained by graft polymerization of a radically polymerizable unsaturated compound having a reactive group to a polyolefin include, for example, maleic anhydride-modified polypropylene and chlorinated products thereof, maleic anhydride-modified propylene-ethylene copolymer and chlorine thereof.
  • a maleic anhydride modified propylene-butene copolymer and its chlorinated product, an acrylic acid modified polypropylene and its chlorinated product, an acrylic acid modified propylene-ethylene copolymer and its chlorinated product, an acrylic acid modified propylene-butene copolymer and Examples thereof include chlorinated substances. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • the radical polymerization initiator used in the graft polymerization can be appropriately selected from ordinary radical initiators, such as organic peroxides such as benzoyl peroxide and t-butylperoxyisopropyl monocarbonate, azonitrile, etc. Can be mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • the method for producing a polymer obtained by graft polymerization of a radically polymerizable unsaturated compound having a reactive group onto a polyolefin is not particularly limited, and any production method may be used.
  • solution modification method method of reacting by heating and stirring in a solution
  • melt modification method method of reacting by melting and heating and stirring without a solvent, or method of reacting by heating and kneading with an extruder
  • a polymer obtained by converting a polyolefin having an unsaturated end group into an element group of group 13 to group 17 is, for example, a double bond of a polyolefin having a terminal double bond as described in JP-A-2001-288372.
  • a polyolefin having part thereof converted into a group 13 element group such as a boron group or an aluminum group, and a double bond part of a polyolefin having a terminal double bond as described in JP-A-2005-48172 is converted into a halogen element.
  • Polyolefin a polyolefin obtained by converting a double bond portion of a propylene-based polymer having a terminal double bond into a mercapto group as described in JP-A-2001-98140 can be used. Usually, a block copolymer is used as a block copolymer. Obtainable.
  • the polymer chain introduced into the hydrophobic polyolefin skeleton via a covalent bond can be used without particular limitation as long as the effects of the present invention are not impaired, depending on the desired physical properties. It may be linear or branched.
  • synthetic polymer such as poly (meth) acrylic resin, polyester resin, polyether resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin, semi-synthetic polymer such as cationic starch, dextrin, hydroxyethyl cellulose, agar, gum arabic, gelatin, etc. Any of these natural polymers can be used.
  • the polymer chain may have a reactive group.
  • the polymer chain is preferably a synthetic polymer because stable physical properties are easily obtained.
  • poly (meth) acrylic resins, polyester resins, polyether resins, polyvinyl alcohol resins, and polyvinylpyrrolidone resins are more preferable, and amphiphilic polyether resins are even more preferable. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • the poly (meth) acrylic resin used for the polymer chain is obtained by polymerizing an unsaturated carboxylic acid or an ester or anhydride thereof by radical polymerization, anionic polymerization, or cationic polymerization.
  • unsaturated carboxylic acid or its ester or anhydride include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, (meth) acrylic acid (dimethyl) Amino) ethyl, (meth) acrylic acid (2-isocyanato) ethyl, maleic anhydride and the like.
  • hydrophobic radical polymerizable compound (hydrophobic monomer) is used in order to provide good adhesion to various thermoplastic resin film substrates within a range that does not impair the effects of the present invention.
  • the copolymerizable hydrophobic monomer include a (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms, an aryl group or an arylalkyl group, and a hydrocarbon group having 1 to 12 carbon atoms. Examples thereof include polymerizable vinyl monomers.
  • the polyvinyl alcohol resin used for the polymer chain can be usually obtained by polymerizing vinyl acetate to obtain polyvinyl acetate and then saponifying.
  • the saponification degree may be complete saponification or partial saponification.
  • the polyvinyl pyrrolidone resin used for the polymer chain can be obtained by polymerizing vinyl pyrrolidone. Of course, a commercially available product may be used.
  • the method for introducing the polymer chain into the polyolefin is not particularly limited.
  • a method of radical polymerization in the presence of a polyolefin, an acrylic system having a reactive group such as a hydroxyl group, an amino group, a glycidyl group, or an (anhydrous) carboxylic acid group examples thereof include a method of reacting a resin with a polyolefin having a reactive group.
  • a polyether resin having amphiphilic properties used as a polymer chain introduced into a hydrophobic polyolefin skeleton via a covalent bond can be obtained by ring-opening polymerization of cyclic alkylene oxide or cyclic alkylene imine.
  • the method for bonding with polyolefin is not particularly limited.
  • a method of ring-opening polymerization of cyclic alkylene oxide in a polyolefin having a reactive group a reaction of polyether polyol or polyether amine obtained by ring-opening polymerization, etc.
  • Examples thereof include a method of reacting a polyether resin having a reactive group with a polyolefin having a reactive group.
  • Polyetheramine is a compound having a primary amino group as a reactive group at one or both ends of a resin having a polyether skeleton.
  • As the polyetheramine Jeffamine M series, D series, ED series, etc. manufactured by Huntsman, USA may be used.
  • Polyether polyol is a compound having hydroxyl groups as reactive groups at both ends of a resin having a polyether skeleton.
  • Preferred examples of the polyalkylene oxide and polyalkyleneimine exhibiting hydrophilicity include polyethylene oxide, polypropylene oxide, and polyethyleneimine.
  • One or more reactive groups may be used, but it is more preferable to have only one reactive group. This is because when there are two or more reactive groups, there is a possibility that a three-dimensional network structure will be formed upon bonding with the polyolefin, resulting in gelation. However, even if it has a plurality of reactive groups, the gelation described above can be avoided if there is only one reactive group having a higher reactivity than others.
  • a hydrophilic polymer having a plurality of hydroxyl groups and one amino group having a higher reactivity is one preferred example. The reactivity here is the reactivity with the reactive group which polyolefin has.
  • an olefin resin marketed as an aqueous dispersion can be preferably used.
  • the Hardren series manufactured by Toyobo Co., Ltd. the Aptolock series manufactured by Mitsubishi Chemical Corporation, the Allobase series manufactured by Unitika Ltd., etc. can be used.
  • the color material used in the present invention is not particularly limited, and color materials usually used in water-based inkjet inks can be used, and examples thereof include pigments and dyes. If the application requires weather resistance and water resistance, it is preferable to use a pigment.
  • a pigment known and commonly used organic pigments or inorganic pigments can be used.
  • the pigment used in the present invention is at least one pigment selected from known and commonly used organic pigments or inorganic pigments.
  • the present invention can be applied to either an untreated pigment or a treated pigment.
  • white ink is also used for the purpose of improving visibility.
  • These pigments used are not particularly limited, and those usually used as pigments for water-based inkjet recording inks can be used. Specifically, it can be dispersed in water or a water-soluble organic solvent, and a known inorganic pigment or organic pigment can be used.
  • organic pigments examples include carbon black produced by a known method such as iron oxide, a contact method, a furnace method, and a thermal method.
  • Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines).
  • Pigments thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (for example, basic dye chelates, acidic dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like.
  • dye chelates for example, basic dye chelates, acidic dye chelates, etc.
  • nitro pigments nitroso pigments, aniline black, and the like.
  • carbon black No. manufactured by Mitsubishi Chemical Corporation. 2300, no. 2200B, no. 900, no. 960, No. 980, no. 33, no. 40, No, 45, No. 45L, no. 52, HCF88, MA7, MA8, MA100, etc. are Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. made by Columbia, and Regal 400R, Regal 330R, Regal 660R, Mull 660R, Mogul made by Cabot. Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc.
  • pigments used in yellow ink include C.I. I. Pigment Yellow 1, 2, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 129, 138, 150, 151, 154, 155, 174, 180, 185 and the like.
  • pigments used in magenta ink include C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 122, 123, 146, 168, 176, 184, 185, 202, 209, etc. It is done.
  • pigments used for cyan ink include C.I. I. Pigment blue 1, 2, 3, 15, 15: 3, 15: 4, 16, 22, 60, 63, 66, and the like.
  • pigments used in white inks include silicas such as alkaline earth metal sulfates, carbonates, finely divided silicic acids, synthetic silicates, calcium silicates, alumina, alumina hydrates, Examples thereof include titanium oxide, zinc oxide, talc, and clay.
  • the inorganic white pigment may be surface-treated by various surface treatment methods.
  • examples of the dye include C.I. I. Acid Black 1, 2, 7, 16, 17, 24, 26, 28, 31, 41, 48, 52, 58, 60, 63, 94, 107, 109, 112, 118, 119, 121, 122, 131, 155, 156; C.I. I. Acid Yellow 1, 3, 4, 7, 11, 12, 13, 14, 17, 18, 19, 23, 25, 29, 34, 38, 40, 41, 42, 44, 49, 53, 55, 59, 61, 71, 72, 76, 78, 79, 99, 111, 114, 116, 122, 135, 142, 161, 172; I. Acid Orange 7, 8, 10, 19, 20, 24, 28, 33, 41, 45, 51, 56, 64; C.I. I.
  • Acid Blue 1 7, 9, 15, 22, 23, 25, 27, 29, 40, 41, 43, 45, 49, 51, 53, 55, 56, 59, 62, 78, 80, 81, 83, 90, 92, 93, 102, 104, 111, 113, 117, 120, 124, 126, 138, 145, 167, 171, 175, 183, 229, 234, 236, 249;
  • Acid Green 3 9, 12, 16, 19, 20, 25, 27, 41, 44; C.I.
  • Acid dyes such as brown 4 and 14
  • a so-called self-dispersing pigment surface-treated pigment having a water dispersibility-imparting group on the pigment surface and capable of stably maintaining the dispersion state without a dispersant
  • So-called capsule pigments water-dispersible polymer-containing pigments
  • the average particle size of the pigment is preferably the particle size normally used for inkjet inks, specifically 50 to 500 nm is preferable, and 50 to 300 nm is more preferable for color inks.
  • the pigment may be dispersed in water using a known and commonly used pigment dispersant or binder, or a surfactant may be used.
  • the pigment dispersant is preferably an aqueous resin, and preferable examples include acrylic resins such as polyvinyl alcohols, polyvinyl pyrrolidones, acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid.
  • Styrene-acrylic such as copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene- ⁇ -methylstyrene-acrylic acid copolymer, styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymer
  • examples thereof include resins, styrene-maleic acid copolymers, styrene-maleic anhydride copolymers, vinylnaphthalene-acrylic acid copolymers, and salts of the aqueous resins.
  • the compounds for forming the copolymer salt include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and diethylamine, ammonia, ethylamine, triethylamine, propylamine, isopropylamine, Examples include propylamine, butylamine, isobutylamine, triethanolamine, diethanolamine, aminomethylpropanol, and morpholine.
  • the amount of the compound used to form these salts is preferably equal to or greater than the neutralization equivalent of the copolymer.
  • Commercially available products include Ajinomoto Fine Techno Co., Ltd. product Ajisper PB series, Big Chemie Japan Co., Ltd. Disperbyk series, BYK-series, EFKA series manufactured by Ciba Specialty Chemicals.
  • the water-soluble solvent and / or water used in the present invention may be water alone or a mixed solvent composed of water and a water-soluble solvent.
  • the water-soluble solvent include ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, and methyl isobutyl ketone; methanol, ethanol, 2-propanol, 2-methyl-1-propanol, 1-butanol, 2-methoxyethanol, Alcohols such as tetrahydrofuran; ethers such as 1,4-dioxane and 1,2-dimethoxyethane; amides such as dimethylformamide and N-methylpyrrolidone, and particularly ketones having 3 to 6 carbon atoms And a compound selected from the group consisting of alcohols having 1 to 5 carbon atoms.
  • the first ink used in the present invention is to prepare a dispersion (pigment paste) of the pigment, dilute it with water, add the resin having the hydroxy group and / or carboxyl group, and wet as necessary.
  • An ink can be prepared by adding an agent (drying inhibitor), a penetrating agent, or other additives.
  • Pigment paste As a method for preparing the pigment paste, the following method can be employed. (1) A method of preparing a pigment paste by adding a pigment to an aqueous medium containing a pigment dispersant and water and then dispersing the pigment in the aqueous medium using a stirring / dispersing device. (2) The pigment and the pigment dispersant are kneaded using a kneader such as two rolls or a mixer, and the resulting kneaded product is added to an aqueous medium containing water, and the pigment is then mixed using a stirring / dispersing device. A method of preparing a paste.
  • the kneader is not particularly limited, and examples thereof include a Henschel mixer, a pressure kneader, a Banbury mixer, and a planetary mixer.
  • the stirring / dispersing device is not particularly limited, and examples thereof include an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disperse mat, an SC mill, and a nanomizer.
  • an ultrasonic homogenizer a high-pressure homogenizer
  • a paint shaker a paint shaker
  • a ball mill a roll mill
  • a sand mill a sand grinder
  • a dyno mill a disperse mat
  • SC mill and a nanomizer.
  • One of these may be used alone, or two or more devices may be used in combination.
  • the amount of pigment in the pigment paste is preferably 5 to 60% by mass, more preferably 10 to 50% by mass.
  • the pigment amount is less than 5% by mass, the water-based ink prepared from the pigment paste is insufficiently colored, and a sufficient image density tends not to be obtained.
  • the amount is more than 60% by mass, the dispersion stability of the pigment tends to decrease in the pigment paste.
  • coarse particles cause nozzle clogging and other image characteristics, and therefore it is preferable to remove the coarse particles by centrifugation or filtration after ink preparation. .
  • the wetting agent is added for the purpose of preventing the ink from drying.
  • the content of the wetting agent in the ink for the purpose of preventing drying is preferably 3 to 50% by mass.
  • the wetting agent used in the present invention is not particularly limited, but a wetting agent that is miscible with water and can prevent clogging of the head of an inkjet printer is preferable.
  • glycerin ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 2000 or less
  • propylene glycol dipropylene glycol, tripropylene glycol, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butane
  • examples include diol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, mesoerythritol, pentaerythritol, and the like.
  • the inclusion of propylene glycol and 1,3-butanediol has safety and excellent effects in ink drying properties and ejection performance.
  • the penetrant is added for the purpose of improving the permeability to a recording medium and adjusting the dot diameter on the recording medium.
  • the penetrant include lower alcohols such as ethanol and isopropyl alcohol, ethylene oxide adducts of alkyl alcohols such as ethylene glycol hexyl ether and diethylene glycol butyl ether, and propylene oxide adducts of alkyl alcohols such as propylene glycol propyl ether.
  • the content of the penetrant in the ink is preferably 0.01 to 10% by mass.
  • the surfactant is added to adjust ink properties such as surface tension.
  • the surfactant that can be added for this purpose is not particularly limited, and examples include various anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Of these, anionic surfactants and nonionic surfactants are preferred.
  • anionic surfactant examples include alkylbenzene sulfonate, alkylphenyl sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfate of higher fatty acid ester, sulfonate of higher fatty acid ester, higher alcohol ether. Sulfate salts and sulfonates of the above, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc.
  • dodecylbenzene sulfonate isopropyl naphthalene sulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenyl sulfonate, dibutylphenylphenol disulfate.
  • phosphate salt can be mentioned.
  • Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester , Polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkyl alkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, Polyethylene glycol polypropylene glycol block copolymer, etc.
  • polyoxyethylene nonyl phenyl ether polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, Fatty acid alkylolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, and polyethylene glycol polypropylene glycol block copolymer are preferred.
  • surfactants include silicone surfactants such as polysiloxane oxyethylene adducts; fluorine surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers.
  • Biosurfactants such as spicrispolic acid, rhamnolipid, lysolecithin and the like can also be used.
  • the HLB is preferably in the range of 7-20.
  • the addition amount is preferably in the range of 0.001 to 2% by mass, more preferably 0.001 to 1.5% by mass, based on the total mass of the ink. More preferably, the content is in the range of 01 to 1% by mass.
  • the addition amount of the surfactant is less than 0.001% by mass, the effect of adding the surfactant tends to be not obtained, and when it exceeds 2% by mass, problems such as blurring of the image are likely to occur. .
  • preservatives can be added as necessary.
  • viscosity modifiers pH adjusters, chelating agents, plasticizers, antioxidants, ultraviolet absorbers and the like can be added as necessary.
  • the amount of pigment in the inkjet recording ink prepared from the pigment paste is 1 to 20% by mass in order to obtain a sufficient image density and to ensure dispersion stability of the pigment in the ink. preferable.
  • the surface tension of the first ink is preferably 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN / m or more and 45 mN / m or less, More preferably, it is 20 mN / m or more and 40 mN / m or less. If the surface tension is less than 20 mN / m, the liquid may overflow on the nozzle surface and printing may not be performed normally. On the other hand, when it exceeds 60 mN / m, there is a tendency that the non-absorbing base material is easily repelled.
  • the viscosity of the first ink is preferably 1.2 mPa ⁇ s or more and 20.0 mPa ⁇ s or less, more preferably 2.0 mPa ⁇ s or more and less than 15.0 mPa ⁇ s, and still more preferably. 3.0 mPa ⁇ s or more and less than 12.0 mPa ⁇ s.
  • the surface tension and viscosity of the first ink can be maintained in the above preferred ranges by adjusting the type and amount of surfactant and water-soluble solvent to be contained.
  • the vinylpyrrolidone N, N-dimethylaminoethyl methacrylate polymer sulfate (A) used in the present invention is represented by the general formula (1), the INCI code is POLYQUATERNIUM-11, and the display name is polyquaternium-11. It is a compound called.
  • the molecular weight of the vinylpyrrolidone / N, N-dimethylaminoethyl methacrylic acid polymer sulfate (A) is preferably in the range of 5,000 to 500,000 in terms of weight average molecular weight, and 10,000 to 200,000. The range of is more preferable. When the weight average molecular weight is less than 5,000, the curing tends to be insufficient, and when it exceeds 500,000, the discharge stability tends to be difficult to ensure.
  • the K value of the vinyl pyrrolidone / N, N-dimethylaminoethyl methacrylic acid polymer sulfate (A) measured by the fixture method is preferably 10 to 100, more preferably 10 to 90. More preferably, it is 10 to 80, and most preferably 10 to 70. Note that the K value measured by the Fikencher method is measured as follows.
  • ⁇ K value> Using ion-exchanged water, a 1% solution of the polymer solution obtained in the following examples was prepared, the viscosity of the solution was measured with a capillary viscometer at 25 ° C., and the obtained value was used by the following Fikencher method. calculate.
  • ⁇ rel is the measured viscosity of the polymer solution (relative viscosity; viscosity of 1% solution of polymer in ion-exchanged water)
  • K o is related to K value. Indicates a variable.
  • vinyl pyrrolidone / N N-dimethylaminoethyl methacrylate polymer sulfate (A)
  • A a commercially available product can be used.
  • HC Polymer series manufactured by Osaka Organic Chemical Industry Co., Ltd., BASF Corporation "Ruby cut PQ11PN” and the like.
  • the vinyl pyrrolidone / N, N-dimethylaminoethyl methacrylic acid polymer sulfate (A) is preferably contained in an amount of 0.1% by mass to 5% by mass in terms of solid content in the second ink. A range of 3% to 3% by weight is still more preferred. If the amount is less than 0.1% by mass, there is a problem that sufficient curing cannot be obtained. If the amount exceeds 3% by mass, the ejection stability is inferior and the image sharpness may be deteriorated.
  • the modified polyethyleneimine (B) used in the present invention may modify polyethyleneimine obtained by polymerizing ethyleneimine by a known method, or may modify commercially available polyethyleneimine.
  • Examples of commercially available polyethyleneimines are commercially available from Nippon Shokubai Co., Ltd. as polyethyleneimine series such as SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000. These can be used either linearly or branched.
  • the modification method may be performed by a known method. For example, it can be modified by reacting an amino group of polyethyleneimine with a compound x having a functional group that reacts with the amino group to form an amide bond at one end.
  • the functional group that reacts with an amino group to form an amide bond by using the compound x having a function to be imparted include a haloformyl group such as a carboxyl group and a chloroformyl group, and an oxycarbonyl group such as a methoxycarbonyl group. .
  • (B-b1) Acrylic copolymer having a functional group reactive with an amino group at one end
  • Bb2) a polyester having a functional group that reacts with an amino group at one end
  • Bb3 Polyamide having a functional group that reacts with an amino group at one end
  • Bb4 Polyesteramide having a functional group that reacts with an amino group at one end Etc.
  • (B-b1) As an acrylic copolymer having a functional group that reacts with an amino group at one end, for example, to obtain a vinyl copolymer having a carboxyl group at one end, a chain transfer agent having a carboxyl group at the time of polymerization is used. The method of making it coexist is mentioned.
  • the chain transfer agent having a carboxyl group include thiocarboxylic acids such as mercaptoacetic acid, 2-mercaptopropionic acid, and 3-mercaptopropionic acid.
  • the polyester having a functional group that reacts with an amino group at one end is specifically a polyester having a carboxyl group at the end.
  • This can be synthesized by various methods as follows. For example, an addition reaction for adding a lactone compound to a monocarboxylic acid compound, an addition reaction for adding a lactone compound to a hydroxycarboxylic acid compound, or a condensation reaction for condensing three components of a monocarboxylic acid compound, a hydroxycarboxylic acid compound, and a lactone compound , Etc.
  • the (Bb3) polyamide having a functional group that reacts with an amino group at one end is specifically a polyamide having a carboxyl group at the end. This is prepared using a lactam such as ⁇ -caprolactam or an aminocarboxylic acid such as aminocaproic acid or 11-aminoundecanoic acid as a raw material.
  • the polyester amide having a functional group that reacts with an amino group at one end is specifically a co-condensate of an ester and an amide having a carboxyl group at the end. This can be prepared by co-condensing hydroxycarboxylic acid, lactone and the like used in the production of the polyester and polyamide with aminocarboxylic acid and lactam.
  • the modified polyethyleneimine (B) is an ethyleneimine in an aqueous medium in the presence of a small amount of an acid or acid-forming compound (eg, a halogenated hydrocarbon such as chloroform, carbon tetrachloride, tetrachloroethane, or ethyl chloride).
  • an acid or acid-forming compound eg, a halogenated hydrocarbon such as chloroform, carbon tetrachloride, tetrachloroethane, or ethyl chloride.
  • a polymer of ethyleneimine obtained by polymerization, or a condensate of epichlorohydrin and an amino group-containing compound for example, monoamine, dimethylamine or diethylamine, ethylenediamine, diethylenetriamine, polyamine such as triethylenetetramine, or ammonia
  • an amino group-containing compound for example, monoamine, dimethylamine or diethylamine, ethylenediamine, diethylenetriamine, polyamine such as triethylenetetramine, or ammonia
  • a compound having a primary amino group or a secondary amino group for example, a graft polymer obtained by grafting a dicarboxylic acid polyamidoamine or polyamine with ethyleneimine can also be used.
  • the polyamidoamine grafted with ethyleneimine may optionally be further reacted with a bifunctional cross-linking agent such as epichlorohydrin or bischlorohydrin ethers of polyalkylene glycols.
  • a polyethyleneimine polymer crosslinked with polyethylene glycol dichlorohydrin ether and neutralized with formic acid is preferably used.
  • Their molar mass Mw is, for example, 500 to 1,000,000, preferably 1,000 to 500,000 g / mol.
  • modified polyethyleneimine (B) a commercially available product can be used as the modified polyethyleneimine (B).
  • B a commercially available product
  • it is sold by BASF under the trade name of Polymin (registered trademark), for example, Polymin (registered trademark) SK.
  • the modified polyethyleneimine (B) is preferably contained in an amount of 0.1% by mass to 5% by mass in terms of solid content in the second ink, and more preferably in the range of 0.3% by mass to 3% by mass. . If the amount is less than 0.1% by mass, there is a problem that sufficient curing cannot be obtained. If the amount exceeds 3% by mass, the ejection stability is inferior and the image sharpness may be lowered.
  • the core-shell type amphoteric emulsion resin (C) used in the present invention is: (Cc1) Cationic polymerizable water-soluble polymer (C-A1), unreacted organic acid group-containing polymerizable compound (CB), and the cationic polymerizable water-soluble polymer (C-A1)
  • Cc1 Cationic polymerizable water-soluble polymer
  • CB unreacted organic acid group-containing polymerizable compound
  • C-A1 cationic polymerizable water-soluble polymer
  • the cationic polymerizable water-soluble polymer (CA1) is a polymer having an amino group-containing polymerizable compound (CA) as an essential polymerization component.
  • Specific examples of the amino group-containing polymerizable compound (CA) include dimethylaminomethyl acrylate, diethylaminomethyl acrylate, dibutylaminomethyl acrylate, dihexylaminomethyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, di (t-butyl).
  • Acrylates such as aminoethyl acrylate, diisohexylaminoethyl acrylate, dihexylaminopropyl acrylate, di (t-butyl) aminohexyl acrylate, and corresponding methacrylates are included. These compounds may be used alone or in a complex system.
  • organic acid group-containing polymerizable compound (CB) examples include acrylic acid, itaconic acid, maleic acid, t-butylacrylamide sulfonic acid, 2-acryloyloxyethyl succinic acid, and 2-acryloyloxyethyl. Included are acrylates such as phthalic acid and the corresponding methacrylates. These may be used alone or in a complex system.
  • polymerizable compound (CC) that does not contain an organic acid group and an amino group
  • alkyl or cycloalkyl esters of acrylic acid or methacrylic acid methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl Monomers such as methacrylate; styrene, vinyltoluene, ⁇ -methylstyrene, vinyl acetate, acrylonitrile, methacrylonitrile, etc.
  • Alkenyl monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, monomers such as hydroxypropyl methacrylate and the like. These may be used alone or in a complex system.
  • the anionic polymerizable water-soluble polymer (CB1) is a polymer containing the organic acid group-containing polymerizable compound (CB) as an essential polymerization component.
  • the cationic polymerizable water-soluble polymer (C-A1) or the anionic polymerizable water-soluble polymer (C-B1) can be obtained by a conventionally known solution polymerization method using a known polymerization initiator. it can.
  • the weight average molecular weight of the copolymer is not particularly limited, but is preferably in the range of 5000 to 50,000.
  • the cationic polymerizable water-soluble polymer (C-A1) is preferably an organic acid group-containing polymerizable compound in a ratio range of 0.5 to 1.5 equivalents relative to 1 equivalent of the amino group of the polymer (C-A1) ( It is obtained by reacting CB). By the above reaction, the amino acid group in the polymer (C-A1) is partially neutralized by the organic acid group-containing polymerizable compound (CB) to become a cationic polymerizable water-soluble polymer (C-A1). . Since the unreacted organic acid group-containing polymerizable compound (CB) is a core component, there is no problem.
  • the anionic polymerizable water-soluble polymer (C-B1) preferably contains an amino group in a ratio range of 0.5 to 1.5 equivalents relative to 1 equivalent of the organic acid group of the polymer (C-B1). It is obtained by reacting a polymerizable compound (CA). By the above reaction, the organic acid group in the polymer (C-B1) is partially neutralized by the amino group-containing polymerizable compound (CA) to become an anionic polymerizable water-soluble polymer (C-A1). . Since the unreacted amino group-containing polymerizable compound (CA) is a core component, there is no problem.
  • the water-soluble polymer (C-A1) or (C-B1) also serves as an emulsifier.
  • a polymerization initiator for emulsion polymerization A well-known redox polymerization initiator can be used, For example, hydrogen peroxide is included.
  • As an emulsion polymerization medium water is preferably used.
  • the emulsion polymerization is preferably performed at a temperature of 60 to 90 degrees.
  • the polymerizable compound (CC) used in the emulsion polymerization is a polymerizable compound containing no acid group and amino group used in the synthesis of the water-soluble polymer (C-A1) or (C-B1). It may be the same as (CC) or different.
  • the core-shell type amphoteric emulsion resin (C) localizes the cationic aqueous polymer and the anionic aqueous polymer in the core part and the shell part, respectively, and is stable depending on whether the shell is an anion or a cation. In addition, adhesion to various substrates is good.
  • the core / shell shell ratio is not particularly limited and may be determined according to desired performance requirements.
  • the core-shell amphoteric emulsion resin (C) may be a commercially available product, for example, a polymer ion complex “Acryt RKW-620” manufactured by Taisei Fine Chemical Co., Ltd.
  • the core-shell type amphoteric emulsion resin (C) is preferably contained in an amount of 0.1% by mass to 5% by mass in terms of solid content in the second ink, and a range of 0.3% by mass to 3% by mass is preferable. Further preferred. If the amount is less than 0.1% by mass, there is a problem that sufficient curing cannot be obtained. If the amount exceeds 3% by mass, the ejection stability is inferior and the image sharpness may be lowered.
  • the second ink used in the present invention may be prepared by appropriately adding a coloring material used in the first ink, a wetting agent (drying inhibitor), a penetrating agent, or other additives. it can.
  • the surface tension of the second ink is preferably 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN / m or more and 45 mN / m or less, More preferably, it is 20 mN / m or more and 40 mN / m or less. If the surface tension is less than 20 mN / m, the liquid may overflow on the nozzle surface and printing may not be performed normally. On the other hand, when it exceeds 60 mN / m, the permeability to the recording medium is lowered and the repelling occurs, so that the image reproducibility tends to be inferior.
  • the viscosity of the second ink is preferably 1.2 mPa ⁇ s or more and 20.0 mPa ⁇ s or less, more preferably 2.0 mPa ⁇ s or more and less than 15.0 mPa ⁇ s, and further preferably 3.0 mPa ⁇ s. s or more and less than 12.0 mPa ⁇ s.
  • the surface tension and viscosity of the second ink can be maintained in the above preferred ranges by adjusting the type and amount of the surfactant and water-soluble solvent to be contained.
  • the water-based ink set for ink-jet recording of the present invention includes at least the first ink and the second ink, and the first ink and the second ink are non-absorbing so that they are in contact with each other. An image is formed on the substrate.
  • Non-absorbing substrate As a plastic film which is a non-absorbing substrate used in the present invention, for example, those used for food packaging materials can be used, and known plastic films can be used. Specific examples include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polyamide films such as nylon, polystyrene films, polyvinyl alcohol films, polyvinyl chloride films, polycarbonate films, polyacrylonitrile films, poly Examples include biodegradable films such as lactic acid films. Polyester film, polyolefin film, and polyamide film are particularly preferable, and polyethylene terephthalate, polypropylene, and nylon are more preferable.
  • the above-mentioned film coated with polyvinylidene chloride or the like for imparting a barrier property may be used, and if necessary, a film in which a deposited layer of a metal oxide such as aluminum or a metal oxide such as silica or alumina is used in combination. May be.
  • the plastic film may be an unstretched film, but is preferably stretched uniaxially or biaxially. Further, the surface of the film may be untreated, but those subjected to various treatments for improving adhesive properties such as corona discharge treatment, ozone treatment, low temperature plasma treatment, flame treatment, glow discharge treatment and the like are preferable.
  • the film thickness of the plastic film is appropriately changed according to the application. For example, in the case of a flexible packaging application, the film thickness is 10 ⁇ m to 100 ⁇ m assuming that it has flexibility, durability, and curl resistance. Preferably there is. More preferably, it is 10 ⁇ m to 30 ⁇ m.
  • the water-based ink set for ink-jet recording according to the present invention includes not only a normal ink-jet recording apparatus but also a recording apparatus equipped with a heater for controlling ink drying or the like, or an intermediate transfer mechanism, and a recording material as an intermediate. It can also be used in a recording apparatus or the like that prints on a recording medium such as a non-absorbing substrate after printing. Any conventionally known method can be used as the ink jet recording method. For example, a method of ejecting droplets using vibration of a piezoelectric element (a recording method using an ink jet head that forms ink droplets by mechanical deformation of an electrostrictive element) or a method of using thermal energy can be given.
  • the first ink and the second ink are applied on the non-absorbing substrate so as to be in contact with each other, there is no particular limitation on the order of the application, and the application of the first ink
  • the second ink may be applied later, the first ink may be applied after the second ink application, or may be applied simultaneously.
  • the application amounts of the first ink and the second ink applied to form one pixel are not necessarily equal, but are within a range of 1:10 to 10: 1 by mass ratio. Thus, it is a preferable aspect to apply ink.
  • NVP-HEA1 282 g of water, 121 g of 2-propanol, and 10 g of N-vinylpyrrolidone were added to a SUS304 reaction vessel (with a cooling tube, a nitrogen introduction line, and a thermometer) as an initial charge.
  • the dissolved oxygen was 0.2 ppm or less.
  • NVP-HEA1 After heating the polymerization vessel to an internal temperature of 80 ° C., a monomer solution in which 182 g of N-vinylpyrrolidone, 41 g of 2-hydroxylethyl acrylate, 0.36 g of triethanolamine, and 97 g of water were mixed with dimethyl-2,2 ′ An initiator solution in which 3.6 g of azobisisobutyrate was dissolved in 31 g of 2-propanol was added dropwise over 150 minutes. Subsequently, a monomer solution in which 7 g of 2-hydroxylethyl acrylate, 5 g of water, and 14 g of 2-propanol were mixed was added over 60 minutes. Thereafter, the jacket was heated and distilled for 90 minutes to obtain a colorless and transparent polymer solution (NVP-HEA1). NVP-HEA1 had a solid content of 40% and a weight average molecular weight of 18,000.
  • magenta pigment dispersion 47 parts of the magenta pigment dispersion, 3 parts of resin (solid content), 15 parts of propylene glycol, 10 parts of 1.3-butanediol, 0.5 part of Surfinol 440, and pure water (remaining amount) are mixed.
  • the mixture was filtered through a 0.5 ⁇ m filter to obtain magenta inks (M-1) to (M-7) and (HM-8).
  • Polymer 2 (trade name): Vinylpyrrolidone / N, N-dimethylaminoethyl methacrylic acid copolymer sulfate (Osaka Organic Chemical Co., Ltd., solid content 20%)
  • Catiofast SF (trade name): modified polyethyleneimine (BASF, solid content 25%)
  • PolyminSK (trade name): Modified polyethyleneimine (BASF, solid content 25%)
  • Epomin SP-018 (trade name): Polyethyleneimine (Nippon Shokubai Co., Ltd.
  • ACRYT RKW-620 (trade name): emulsion containing core-shell type acrylic amphoteric copolymer particles (manufactured by Taisei Fine Chemical Co., Ltd., pH 5.2, solid content 29%)
  • PAA-01 (trade name): allylamine polymer (manufactured by Nitto Bo Medical Co., Ltd.), molecular weight 1,600, concentration 15%, pH: 11
  • PAA-1112 (trade name): Allylamine / dimethylallylamine copolymer (manufactured by Nitto Bo Medical Co., Ltd.) Molecular weight 1,000, concentration: 15%, pH: 11
  • the acid value was measured by a method based on JIS K0070.
  • A is the acid value of the resin (mgKOH / g)
  • B is the amount of 0.1 mol / L potassium hydroxide ethanol solution used for titration (ml)
  • f is the 0.1 mol / liter potassium hydroxide ethanol solution.
  • S is the mass (g) of the resin
  • 5.611 is a value (56.11 / 10) of 1/10 of the formula weight of potassium hydroxide.
  • the hydroxyl value was measured by a method based on JIS K0070.
  • the solvent shown below was used as a solvent for a measurement. 3 g of resin obtained by drying and solidifying the above resin aqueous solution is weighed into a 100 ml Erlenmeyer flask, 10.0 ml of acetic anhydride solution is added and stirred for 15 minutes. Add 2 ml of water and 10.0 ml of pyridine + water (3 + 1) and stir for 5 minutes.
  • A is the hydroxyl value of the resin (mgKOH / g)
  • B is a blank value
  • C is the amount of 0.5 mol / l potassium hydroxide ethanol aqueous solution used for titration (ml)
  • f is the factor of the titrant
  • D Is a concentration conversion factor
  • E is a unit conversion factor
  • S is a sampled amount.
  • the DSC measurement was performed at a heating rate of 5 ° C./min according to JIS7122 using a thermal analyzer DSC10 manufactured by DuPont.
  • Mw of a resin having a hydroxyl group and / or a carboxyl group was determined by GPC measurement under the following conditions.
  • Examples 1 to 168, Comparative Examples 1 to 4 Each ink set was loaded into an ink jet recording apparatus (EB-100 manufactured by Konica Minolta Co., Ltd.) having 256 nozzles ⁇ 2 rows of piezo-type ink jet nozzles, and an OPP film (FOR # manufactured by Futamura Chemical Co., Ltd.) was used as a recording material. 20 and a film thickness of 20 ⁇ m).
  • the droplet size was about 42 pl so that it could be ejected at a resolution of 360 ⁇ 360 dpi (dpi is the number of dots per 2.54 cm) and was driven at a driving frequency of 2 kHz. While preheating with a heater so that the surface of the film was about 60 ° C., printing was performed according to the following ink application sequence, followed by drying (80 ° C./60 seconds).
  • Type A The second ink is applied after the first ink is applied.
  • Type B The first ink is applied after the second ink is applied.
  • Type C First ink and second ink are applied simultaneously.
  • Viscosity measurement method Using an E-type viscometer “V-25 type (manufactured by Toki Sangyo Co., Ltd.)”, measurement was performed (ink temperature 25 ° C.).
  • PH measurement method Measurement was performed using MM-60R (manufactured by Toa DKK Co., Ltd.) (ink temperature 25 ° C.).
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having a hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone ⁇ N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink mixing ratio mass ratio: Resin having hydroxy group and / or carboxyl group (solid content) / vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate polymer sulfate (A), modified polyethyleneimine polymer (B), And at least one polymer (solid content) selected from the group consisting of a core-shell amphoteric emulsion polymer (C)
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Ink application order type A Application of the second ink after application of the first ink
  • Type B Application of the first ink after application of the second ink
  • Type C Application of the first ink and the second ink simultaneously
  • Comparative Examples 1 to 5 in the case where a resin having no hydroxy group and carboxyl group was used as the binder resin in the first ink, the evaluation of the printed matter was x.
  • Comparative Examples 6 to 14 are vinylpyrrolidone / N, N-dimethylaminoethyl methacrylic acid copolymer sulfate (A) and / or modified polyethyleneimine polymer (B) and / or core-shell type acrylic resin amphoteric copolymer particles. Although it is an example which does not have (C), the desired effect was not acquired.

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

Abstract

L'invention concerne un jeu d'encres aqueuses pour enregistrement par jet d'encre utilisant au moins deux types d'encre et caractérisé en ce qu'il comprend : une première encre comprenant une résine, un solvant soluble dans l'eau et/ou de l'eau, ladite résine ayant une matière colorante, un groupe hydroxy et/ou un groupe carboxyle ; et une seconde encre comprenant au moins un polymère, un solvant soluble dans l'eau et/ou de l'eau, ledit polymère étant choisi dans un groupe comprenant un sulfate de polymère vinylpyrrolidone·méthacrylate de N, N‑diméthylaminoéthyle (A), un polymère de polyéthylèneimine modifié(B), et un polymère en émulsion amphotère de type cœur-écorce(C).
PCT/JP2013/062449 2012-05-29 2013-04-26 Jeu d'encres aqueuses pour enregistrement par jet d'encre WO2013179838A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2013540126A JP5500410B1 (ja) 2012-05-29 2013-04-26 インクジェット記録用水性インクセット

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-121905 2012-05-29
JP2012121905 2012-05-29

Publications (1)

Publication Number Publication Date
WO2013179838A1 true WO2013179838A1 (fr) 2013-12-05

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019131541A1 (fr) * 2017-12-26 2019-07-04 花王株式会社 Dispersion de particules de résine
WO2023105737A1 (fr) * 2021-12-10 2023-06-15 コニカミノルタ株式会社 Jeu d'encre pour impression à jet d'encre, procédé d'impression à jet d'encre et dispositif d'impression à jet d'encre

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08216498A (ja) * 1995-02-13 1996-08-27 Canon Inc 画像形成方法、これを用いた画像形成装置及び画像形成物
JP2007276387A (ja) * 2006-04-11 2007-10-25 Ricoh Co Ltd インクメディアセット、並びに前処理液カートリッジ、インクカートリッジ、インク記録物、インクジェット記録方法、及びインクジェット記録装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08216498A (ja) * 1995-02-13 1996-08-27 Canon Inc 画像形成方法、これを用いた画像形成装置及び画像形成物
JP2007276387A (ja) * 2006-04-11 2007-10-25 Ricoh Co Ltd インクメディアセット、並びに前処理液カートリッジ、インクカートリッジ、インク記録物、インクジェット記録方法、及びインクジェット記録装置

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019131541A1 (fr) * 2017-12-26 2019-07-04 花王株式会社 Dispersion de particules de résine
JP2019116535A (ja) * 2017-12-26 2019-07-18 花王株式会社 樹脂粒子分散体
JP7001222B2 (ja) 2017-12-26 2022-01-19 花王株式会社 樹脂粒子分散体
WO2023105737A1 (fr) * 2021-12-10 2023-06-15 コニカミノルタ株式会社 Jeu d'encre pour impression à jet d'encre, procédé d'impression à jet d'encre et dispositif d'impression à jet d'encre

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JPWO2013179838A1 (ja) 2016-01-18

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