WO2012056932A1 - Procédé de production d'une composition d'encre noire - Google Patents

Procédé de production d'une composition d'encre noire Download PDF

Info

Publication number
WO2012056932A1
WO2012056932A1 PCT/JP2011/073857 JP2011073857W WO2012056932A1 WO 2012056932 A1 WO2012056932 A1 WO 2012056932A1 JP 2011073857 W JP2011073857 W JP 2011073857W WO 2012056932 A1 WO2012056932 A1 WO 2012056932A1
Authority
WO
WIPO (PCT)
Prior art keywords
pigment
ink composition
water
aqueous dispersion
carbon black
Prior art date
Application number
PCT/JP2011/073857
Other languages
English (en)
Japanese (ja)
Inventor
松本　淳
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Publication of WO2012056932A1 publication Critical patent/WO2012056932A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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 a method for producing a black ink composition.
  • Inkjet technology has been applied as an image recording method for recording color images in the fields of office printers, home printers, and the like.
  • a pigment is widely used as a colorant for an ink component used in inkjet.
  • carbon black is often used for black ink.
  • a black ink composition using carbon black is capable of improving the hue by using a color pigment in combination with carbon black (see, for example, JP 2000-318293 A).
  • organic solvent-based UV curable inks it has been studied to add a phthalocyanine derivative to black ink in order to improve storage stability and curability (see, for example, JP-A-2005-264098).
  • water-based inks are preferable for reducing the environmental load.
  • water-based pigment inks do not necessarily have sufficient scratch resistance and the like, recently, ultraviolet curable water-based pigment inks have been studied.
  • JP-A-2005-264098 contributes to the improvement of the dispersibility of the carbon black pigment, and is essentially different from a so-called pigment intended for coloring.
  • the present invention provides a method for producing a black ink composition for ink-jet recording, which can be excellent in ejection stability and can form an image excellent in adhesion to a recording medium.
  • ⁇ 1> Obtaining an aqueous carbon black pigment dispersion containing a carbon black pigment as a pigment, and an aqueous pigment dispersion containing at least one color pigment selected from the group consisting of a magenta pigment, a cyan pigment and a yellow pigment as a pigment And mixing a carbon black pigment aqueous dispersion, the color pigment aqueous dispersion, a water-soluble polymerizable compound, and a polymerization initiator, to produce a black ink composition for inkjet recording Method.
  • At least one of the carbon black pigment aqueous dispersion and the colored pigment aqueous dispersion contains a pigment coated with a water-insoluble resin having an acidic group on at least a part of the surface thereof.
  • ⁇ 3> The method for producing a black ink composition according to ⁇ 1> or ⁇ 2>, wherein the colored pigment aqueous dispersion contains at least one color pigment selected from the group consisting of a magenta pigment and a cyan pigment. .
  • ⁇ 4> The method for producing a black ink composition according to any one of ⁇ 1> to ⁇ 3>, wherein the polymerization initiator is a compound represented by the following general formula (1).
  • n each independently represent an integer of 0 or more, and m + n represents an integer of 0 to 3)
  • ⁇ 5> The above ⁇ 1> to ⁇ 4>, further comprising mixing colloidal silica with the carbon black pigment aqueous dispersion, the color pigment aqueous dispersion, the water-soluble polymerizable compound, and the polymerization initiator.
  • the volume average secondary particle diameter of the pigment contained in at least one selected from the group consisting of the carbon black pigment aqueous dispersion and the color pigment aqueous dispersion is 40 nm to 150 nm, ⁇ 1> to ⁇ 5.
  • ⁇ 7> The above-mentioned ⁇ 1>, further comprising mixing an acetylene glycol surfactant with the carbon black pigment aqueous dispersion, the colored pigment aqueous dispersion, the water-soluble polymerizable compound, and the polymerization initiator.
  • the method for producing a black ink composition according to any one of to ⁇ 6>.
  • the present invention it is possible to provide a method for producing a black ink composition for ink jet recording capable of forming an image having excellent ejection stability and excellent adhesion to a recording medium.
  • step includes not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the intended effect of the step is achieved. To do.
  • a numerical range (X and Y are numerical values) indicated in the format of “X to Y” means a range including X as a minimum value and Y as a maximum value.
  • the method for producing a black ink composition for ink jet recording of the present invention includes obtaining a carbon black pigment aqueous dispersion containing a carbon black pigment as a pigment, a magenta pigment, Obtaining an aqueous dispersion of a colored pigment containing, as a pigment, at least one color pigment selected from the group consisting of a cyan pigment and a yellow pigment, the aqueous dispersion of the carbon black pigment, the aqueous dispersion of the colored pigment, and a water-soluble polymerization Mixing the active compound and the polymerization initiator.
  • the manufacturing method may or may not include other steps as necessary.
  • the manufacturing method comprises a step of obtaining an aqueous dispersion containing at least one color pigment selected from the group consisting of a magenta pigment, a cyan pigment and a yellow pigment, independently of the step of obtaining an aqueous dispersion of a carbon black pigment.
  • a black ink composition that can be excellent in ejection stability can be produced.
  • an image having excellent adhesion to the recording medium can be formed.
  • the aqueous dispersion of carbon black pigment is typically obtained by a step of dispersing the carbon black pigment in an aqueous medium.
  • the carbon black dispersion step is not particularly limited as long as the carbon black pigment can be dispersed in an aqueous medium, and a commonly used dispersion method can be appropriately selected and applied.
  • an aqueous carbon black pigment dispersion can be obtained by mixing at least one dispersant and at least one carbon black pigment in an aqueous medium, and dispersing the resulting mixture.
  • the mixing method and the dispersion treatment method are not particularly limited, and a commonly used mixing and stirring device, and a dispersing device such as an ultrasonic dispersing machine, a high-pressure homogenizer, a ball mill, a roll mill, and a high-speed stirring type dispersing machine may be used as necessary. it can.
  • a dispersing device such as an ultrasonic dispersing machine, a high-pressure homogenizer, a ball mill, a roll mill, and a high-speed stirring type dispersing machine may be used as necessary. it can.
  • the dispersant may be either a polymer dispersant or a low molecular surfactant type dispersant.
  • the polymer dispersant may be either a water-soluble dispersant or a water-insoluble dispersant.
  • the low molecular surfactant type dispersant a commonly used low molecular surfactant can be used without particular limitation.
  • examples of the water-soluble dispersant include hydrophilic polymer compounds.
  • natural hydrophilic polymer compounds include plant polymers such as gum arabic, tragan gum, guar gum, karaya gum, locust bean gum, arabinogalactone, pectin, quince seed starch, seaweeds such as alginic acid, carrageenan and agar.
  • examples include molecules, animal polymers such as gelatin, casein, albumin and collagen, and microorganism polymers such as xanthene gum and dextran.
  • fiber polymers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and carboxymethylcellulose
  • starch starches such as sodium starch glycolate and sodium phosphate phosphate
  • examples include molecules, seaweed polymers such as sodium alginate and propylene glycol alginate.
  • Synthetic hydrophilic polymer compounds include vinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl methyl ether, non-crosslinked polyacrylamides, polyacrylic acid or alkali metal salts thereof, and acrylics such as water-soluble styrene acrylic resins. Resin, water-soluble styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic resin, polyvinyl pyrrolidone, polyvinyl alcohol, alkali metal salt of ⁇ -naphthalene sulfonic acid formalin condensate, quaternary ammonium, amino group, etc. And a polymer compound having a cationic functional group salt in the side chain, a natural polymer compound such as shellac, and the like.
  • water-soluble dispersants introduced with carboxyl groups such as homopolymers such as acrylic acid, methacrylic acid, and styrene acrylic acid, and copolymers with monomers having other hydrophilic groups are highly hydrophilic. Preferred as a molecular compound.
  • water-insoluble dispersant among the polymer dispersants a water-insoluble resin having a hydrophobic constituent unit and a hydrophilic constituent unit can be used.
  • hydrophilic structural unit a structural unit having an acidic group is preferable, and a structural unit having a carboxyl group is more preferable.
  • water-insoluble resins include styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, (meth) acrylic acid ester- (meth) acrylic acid copolymer.
  • Examples thereof include a polymer, a polyethylene glycol (meth) acrylate- (meth) acrylic acid copolymer, a vinyl acetate-maleic acid copolymer, and a styrene-maleic acid copolymer. More specifically, for example, water-insoluble resins described in JP-A-2005-41994, JP-A-2006-273891, JP-A-2009-084494, JP-A-2009-191134, and the like can be suitably used. .
  • the carbon black dispersion step uses a water-insoluble resin having an acidic group as a dispersant, and a mixture containing the carbon black pigment, a neutralizing agent, water, and a water-soluble organic solvent capable of dissolving or dispersing the water-insoluble resin.
  • the method includes a step of dispersing the mixture, a step of dispersing the mixture, and a step of removing at least a part of the water-soluble organic solvent after the dispersion treatment step.
  • phase inversion emulsification method Such a dispersion method is generally called a phase inversion emulsification method.
  • phase inversion emulsification method For details of the phase inversion emulsification method, reference can be made to, for example, descriptions in JP-A-10-140065, JP-A-11-209672, JP-A-11-172180, and the like.
  • the water-insoluble resin used for phase inversion emulsification preferably contains a water-insoluble resin having a carboxyl group, from the viewpoint of self-dispersibility and the aggregation rate when the treatment liquid described below comes into contact, and has a carboxyl group, A water-insoluble resin having an acid value of 100 mgKOH / g or less is preferable, and a water-insoluble resin having an acid value of 25 to 100 mgKOH / g is more preferable.
  • a polymer dispersant having a carboxyl group and having an acid value of 25 to 100 mgKOH / g may be effective.
  • the weight average molecular weight of the water-insoluble resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 40,000, and particularly preferably 10 , 40,000.
  • the mixing method and the dispersion method in the phase inversion emulsification method are not particularly limited. Dispersion of a generally used mixing and stirring device, ultrasonic dispersing machine, high-pressure homogenizer, ball mill, roll mill, high-speed stirring type dispersing machine, etc. An apparatus can be used.
  • the water-soluble organic solvent used in the phase inversion emulsification method is not particularly limited as long as the water-insoluble resin can be dissolved or dispersed, and can be appropriately selected according to the water-insoluble resin.
  • Specific examples include alcohol solvents, ketone solvents, and ether solvents.
  • the alcohol solvent include isopropyl alcohol, n-butanol, t-butanol, ethanol and the like.
  • the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone.
  • the ether solvent include dibutyl ether and dioxane.
  • ketone solvents such as methyl ethyl ketone and alcohol solvents such as isopropyl alcohol are preferable, and ketone solvents such as methyl ethyl ketone are more preferable.
  • the neutralizing agent is used to form an emulsified state or a dispersed state in which a part or all of acidic groups are neutralized and the water-insoluble resin is stable in water.
  • the neutralizing agent include alcohol amines (eg, diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol), alkali metal hydroxides (eg, lithium hydroxide, hydroxide) Sodium, potassium hydroxide, etc.), ammonium hydroxide (eg, ammonium hydroxide, quaternary ammonium hydroxide), phosphonium hydroxide, alkali metal carbonate, etc.
  • alcohol amines eg, diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol
  • alkali metal hydroxides eg, lithium hydroxide, hydroxide
  • ammonium hydroxide eg, ammoni
  • the carbon black pigment dispersion step is a method for obtaining “a pigment dispersion in which at least a part of the pigment surface is coated with a water-insoluble resin”, and after dispersing the pigment using a water-soluble or water-insoluble dispersant.
  • the pigment dispersion is prepared by crosslinking the dispersant with a crosslinking agent to insolubilize the water-soluble dispersant.
  • the dispersant include polyvinyls, polyurethanes, polyesters, etc. Among them, polyvinyls are preferable.
  • the dispersant needs to have a functional group that can be crosslinked by a crosslinking agent in the molecule.
  • the crosslinkable functional group is not particularly limited, and examples thereof include a carboxyl group or a salt thereof, an isocyanate group, an epoxy group, and the like. From the viewpoint of improving dispersibility, the functional group may have a carboxyl group or a salt thereof. preferable.
  • the dispersant is preferably a copolymer obtained using a carboxyl group-containing monomer as a copolymerization component.
  • the carboxyl group-containing monomer include (meth) acrylic acid, ⁇ -carboxyethyl acrylate, fumaric acid, itaconic acid, maleic acid, crotonic acid and the like.
  • (meth) Acrylic acid and ⁇ -carboxyethyl acrylate are preferred.
  • (Meth) acrylic acid means at least one of acrylic acid and methacrylic acid.
  • the copolymer component preferably contains at least one hydrophobic monomer.
  • hydrophobic monomers examples include alkyl (meth) acrylates having 1 to 20 carbon atoms, (meth) acrylates having an aromatic ring group such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate, and styrene and its derivatives. Can be mentioned.
  • the dispersant is a copolymer obtained by using a carboxyl group-containing monomer and at least one of an alkyl (meth) acrylate having 1 to 20 carbon atoms and a (meth) acrylate having an aromatic ring group as a copolymerization component.
  • the method for synthesizing the copolymer as a dispersant is not particularly limited, but random polymerization of vinyl monomers is preferable from the viewpoint of dispersion stability.
  • the acid value of the dispersant before crosslinking is preferably 60 to 250 mgKOH / g, more preferably 65 to 150 mgKOH / g, from the viewpoint of dispersibility of the pigment.
  • the acid value of the dispersant after crosslinking is preferably 25 to 100 mgKOH / g from the viewpoints of stability and ink aggregation.
  • the weight average molecular weight of the dispersant before crosslinking is not particularly limited, but is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, from the viewpoint of dispersibility of the pigment. , 40,000 is more preferable.
  • the cross-linking agent is not particularly limited as long as it is a compound having two or more sites that react with the dispersant, but preferably has two or more epoxy groups from the viewpoint of excellent reactivity with a carboxyl group.
  • a compound having bifunctionality (a bifunctional or higher functional epoxy compound) is preferred. Specific examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl.
  • Examples include ether and trimethylolpropane triglycidyl ether, and polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether are preferable.
  • the molar ratio of the crosslinking site of the crosslinking agent to the crosslinked site of the dispersant is preferably from 1: 1.1 to 1:10, from the viewpoint of the crosslinking reaction rate and the dispersion stability after crosslinking, 1: 5 is more preferable, and 1: 1.1 to 1: 3 is most preferable.
  • a pigment dispersion in which at least a part of the pigment surface is coated with a water-insoluble resin can be produced by the method described in JP-A-2009-190379.
  • the mixing mass ratio (p: s) between the carbon black pigment (p) and the dispersant (s) is not particularly limited, and can be appropriately selected according to the dispersion method and the like.
  • a range of 1: 0.06 to 1: 3 is preferable, a range of 1: 0.125 to 1: 1 is more preferable, and a range of 1: 0.125 to 1: 0.7 is more preferable.
  • the average particle size of the carbon black pigment in the dispersed state is preferably 10 to 200 nm, more preferably 10 to 150 nm, and further preferably 40 to 150 nm.
  • the particle size distribution of the carbon black pigment aqueous dispersion is not particularly limited, and may be either a wide particle size distribution or a monodisperse particle size distribution. In some embodiments, only one or a mixture of two or more carbon black pigment aqueous dispersions having a monodisperse particle size distribution may be used.
  • the average particle diameter of the carbon black pigment in a dispersed state means the average particle diameter in an ink state. The same applies to the average particle size of the carbon black pigment in the so-called concentrated ink dispersion before ink conversion.
  • the average particle size and particle size distribution of the carbon black pigment in the dispersed state were measured by a dynamic light scattering method using a nanotrack particle size distribution analyzer UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.). It is calculated
  • Carbon black pigment There is no restriction
  • TEM2010 transmission electron microscope TEM2010 (trade name, pressurization voltage 200 kV) manufactured by JEOL Ltd.
  • the pH of the carbon black pigment is preferably in the acidic to neutral range because easy dispersibility is obtained, more preferably pH 2.0 to pH 8.5, and pH 2.5 to pH 8.0. It is particularly preferred.
  • the pH of the carbon black pigment is measured as the pH (25 ° C.) of the aqueous dispersion of the carbon black pigment.
  • the DBP absorption amount of the carbon black pigment is not particularly limited, but is preferably 30 ml / 100 g or more and 200 ml / 100 g or less, and more preferably 50 ml / 100 g or more and 150 ml / 100 g or less from the viewpoint of color tone and printing density. .
  • the DBP absorption is measured by JIS K6221 A method.
  • the BET specific surface area of the carbon black pigment is not particularly limited, but is preferably 30 m 2 / g or more and 450 m 2 / g or less, and 200 m 2 / g or more and 400 m 2 / g or less from the viewpoint of printing density and storage stability. It is more preferable that
  • Examples of the carbon black pigment include those produced by known methods such as a contact method, a furnace method, and a thermal method. Specific examples include, for example, Raven7000, Raven5750, Raven5250, Raven5000ULTRAII, Raven3500, Raven2000, Raven1500, Raven1250, Raven1200, Raven1190 ULTRAII, Raven1170, Raven1255, Raven10, Raven10 REGAL400R, REGAL330R, REGAL660R, MOGUL L, BLACK PEARLS L, MONARCH 700, MONARCH 800, MONARCH 880, MONARCH 900, MONARCH 1000, MONARCH 1100, MONARCH 1300, M NARCH 1400 (above, manufactured by Cabot Corporation), COLOR BLACK FW1, COLOR BLACK FW2, COLOR BLACK FW2V, COLOR BLACK 18, COLOR BLACK FW200, COLOR BLACK S150, COLOR BLACK TE 160, COLOR BLTE TE 160, COLOR BLS PRINTE
  • the above carbon black pigments may be used singly or in combination of two or more.
  • the content of the carbon black pigment with respect to the total mass of the ink composition is not particularly limited, but is preferably 0.5 to 4% by mass from the viewpoint of adhesion to a recording medium, abrasion resistance, and print density. 0.8 to 2% by mass is more preferable.
  • the colored pigment aqueous dispersion is typically obtained by dispersing the colored pigment in an aqueous medium.
  • the color pigment dispersion step is not particularly limited as long as at least one color pigment selected from a magenta pigment, a cyan pigment, and a yellow pigment can be dispersed in an aqueous medium, and a commonly used dispersion method is appropriately selected and applied. can do.
  • an aqueous colored pigment dispersion can be obtained by mixing at least one dispersing agent and at least one coloring pigment in an aqueous medium and dispersing the resulting mixture.
  • the dispersant, the mixing method, and the dispersion treatment method are as described above.
  • the colored pigment is dispersed to prepare an aqueous colored pigment dispersion, and an ink composition is produced using the dispersion.
  • a black ink composition that can be more excellent in dispersion stability and ejection stability can be produced.
  • This effect can be considered to be obtained because, for example, the aqueous pigment dispersion can be made into a better dispersion state according to the type of pigment.
  • the manufacturing method it is possible to select more appropriate dispersion conditions depending on the type of pigment.
  • the color pigment dispersion step may be a step of mixing and co-dispersing two or more types of color pigments for each color pigment. It may be a step of monodisperse processing. In an embodiment, from the viewpoint of ejection stability, it is preferable to prepare an aqueous colored pigment dispersion for each colored pigment.
  • the color pigment dispersion step uses the water-insoluble resin having the acidic group as a dispersant, obtains a mixture containing the color pigment, a neutralizing agent, water, and a water-soluble organic solvent, and disperses the mixture. And a step of removing at least a part of the water-soluble organic solvent after the dispersion treatment step.
  • an aqueous colored pigment dispersion that can be excellent in dispersion stability can be obtained.
  • the dispersant may be water-insolubilized by crosslinking the dispersant using a cross-linking agent to produce a dispersion. This is a preferred embodiment.
  • the details of the color pigment dispersion step are the same as those in the carbon black dispersion step, and the preferred embodiments are also the same.
  • the average particle diameter of the colored pigment in the dispersed state is preferably 10 to 200 nm, more preferably 10 to 150 nm, and further preferably 40 to 150 nm.
  • the particle size distribution of the color pigment aqueous dispersion is not particularly limited, and may be either a wide particle size distribution or a monodisperse particle size distribution. In an embodiment, the color pigment aqueous dispersion having a monodisperse particle size distribution may be used alone or in combination of two or more.
  • the colored pigment in the present invention is at least one selected from a magenta pigment, a cyan pigment, and a yellow pigment.
  • the magenta pigment, cyan pigment, and yellow pigment can be appropriately selected from known organic pigments according to the purpose. Specific examples of the organic pigment are shown below.
  • magenta pigments examples include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I.
  • cyan pigments examples include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. Pigment Green 7, and siloxane-crosslinked aluminum phthalocyanine described in US Pat. No. 4,311,775.
  • C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. C.I. preferably at least one selected from CI Pigment Blue 16.
  • yellow pigment examples include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 180, C.I. I. And CI Pigment Yellow 185.
  • C.I. I. Pigment yellow 74 C.I. I. Pigment yellow 155, C.I. I. It is preferably at least one selected from Pigment Yellow 185.
  • the color pigment preferably contains at least one magenta pigment and at least one cyan pigment from the viewpoint of adhesion to a recording medium.
  • the content of the color pigment relative to the total mass of the carbon black pigment and the color pigment is not particularly limited. From the viewpoints of adhesion to a recording medium, abrasion resistance, and ejection properties, the content is preferably 5% by mass to 60% by mass, and more preferably 10% by mass to 50% by mass.
  • the content of the magenta pigment (magenta pigment / cyan pigment) with respect to the content of the cyan pigment in the ink composition is not particularly limited. From the viewpoints of adhesion to a recording medium, abrasion resistance, and color tone, it is preferably 100% by mass or more and 180% by mass or less, and more preferably 120% by mass or more and 150% by mass or less.
  • the mixture obtained in the mixing step may or may not be filtered.
  • the method for the filtration treatment is not particularly limited, and any of atmospheric filtration, pressure filtration, suction filtration and the like may be used.
  • the filter medium used for filtration is not particularly limited, and can be appropriately selected according to the purpose. Examples thereof include filter paper and membrane filter.
  • a water-soluble polymerizable compound is used for mixing.
  • water-soluble means a property that can be dissolved in water so as to have a certain concentration or more.
  • the solubility in water at 25 ° C. is preferably 5% by mass or more, and more preferably 10% by mass or more.
  • the water-soluble polymerizable compound is preferably one that can be dissolved (desirably uniformly) in the aqueous ink composition.
  • the solubility may be increased by adding a water-soluble organic solvent to be described later, and it may be dissolved (desirably uniformly) in the ink composition or not.
  • the water-soluble polymerizable compound preferably contains at least one selected from the group consisting of a compound having a (meth) acrylic ester structure in the molecule and a compound having a (meth) acrylamide structure in the molecule. It is more preferable to contain at least one compound having a (meth) acrylamide structure.
  • the (meth) acrylic ester structure means at least one of a methacrylic ester structure and an acrylic ester structure
  • the (meth) acrylamide structure means at least one of a methacrylamide structure and an acrylamide structure.
  • the polymerizable compound having a (meth) acrylic ester structure in the molecule is not limited as long as it is a polymerizable compound having a (meth) acrylic ester structure in the molecule.
  • the polymerizable compound having a (meth) acrylic ester structure in the molecule is preferably a compound represented by the following general formula (M-1).
  • Q 1 represents an i-valent linking group
  • R 1 represents a hydrogen atom or a methyl group
  • I represents an integer of 1 or more.
  • Compound represented by the general formula (M-1) are those unsaturated monomer bonded to the linking group Q 1 by an ester bond.
  • R 1 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
  • the valence i of the linking group Q 1 preferably 2 or more, more preferably 2 to 6 or less, still more preferably 2 to 4.
  • the linking group Q 1 is not particularly limited as long as it is a group that can be linked to the (meth) acrylic ester structure, but is selected from the linking groups such that the compound represented by the general formula (M-1) satisfies the aforementioned water solubility. It is preferred that Specific examples include residues from which one or more hydrogen atoms or hydroxyl groups have been removed from the following compound group X.
  • Still linking group Q 1 methylene, ethylene, propylene, 4 or less of the substituted or unsubstituted alkylene chain of carbon atoms such as butylene group, more pyridine ring, an imidazole ring, a pyrazine ring, piperidine ring, piperazine ring, morpholine ring Examples thereof include a functional group having a saturated or unsaturated heterocyclic ring.
  • the linking group Q 1 is preferably a residue of a polyol containing an oxyalkylene group (preferably an oxyethylene group), and contains three or more oxyalkylene groups (preferably an oxyethylene group).
  • a residue of a polyol is particularly preferable.
  • water-soluble polymerizable compound (M-1) having a (meth) acrylic ester structure in the molecule include, for example, the following nonionic compounds, but the present application is not limited thereto.
  • nonionic polymerizable compound a (meth) acrylic acid ester having two or more acryloyl groups in one molecule derived from a polyol compound can also be used.
  • the polyol compound include polyol compounds having two or more hydroxyl groups such as glycol condensates, oligoethers, oligoesters, monosaccharides, and disaccharides.
  • (meth) acrylic acid esters with triethanolamine, diethanolamine, trishydroxyaminomethane, trishydroxyaminoethane, etc. are also suitable.
  • water-soluble polymerizable compound (M-1) having a (meth) acrylic ester structure in the molecule include the following cationic compounds. It is not limited.
  • R represents a residue of a polyol compound.
  • X represents H or CH 3
  • a ⁇ represents Cl ⁇ , HSO 4 — or CH 3 COO — .
  • the polyol compound include glycerin, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, trimethylolpropane, trimethylolmethane, trimethylolethane, penta Examples include erythritol, bisphenol A, alicyclic bisphenol A, and condensates thereof.
  • the following structures (cationic compounds 1 to 11) can also be exemplified as the polymerizable compound having a cationic group.
  • the compound having a (meth) acrylamide structure in the molecule is not limited as long as it is a polymerizable compound having a (meth) acrylamide structure in the molecule.
  • the compound having a (meth) acrylamide structure in the molecule is preferably a compound represented by the following general formula (M-2). Having the structure of the formula (M-2) is preferable because the compatibility between the compound represented by the general formula (1) described later and the polymerizable compound is improved, and the curing sensitivity and the like can be increased.
  • Q 2 represents a j-valent linking group
  • R 2 represents a hydrogen atom or a methyl group
  • J represents an integer of 1 or more.
  • the compound represented by formula (M-2) are those unsaturated monomers, bonded to the linking group Q 2 by an amide bond.
  • R 2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
  • the linking group Q is not limited to two valence j, preferably 2 or more, more preferably 2 to 6 or less, still more preferably 2 to 4.
  • the connecting group Q 2 is not particularly limited as long as it is capable of linking groups and (meth) acrylamide structure. Details of the linking group Q 2 is the same as the linking group Q 1, preferred embodiment is also the same.
  • water-soluble polymerizable compound having a (meth) acrylamide structure in the molecule include the following water-soluble polymerizable compounds.
  • a compound having a maleimide structure represented by the following a compound having a sulfamide structure, a compound having an N-vinylacetamide structure, or the like can be used.
  • a water-soluble polymeric compound can be contained individually by 1 type or in combination of 2 or more types.
  • the content of the polymerizable compound in the ink composition is preferably 3 to 50% by mass, more preferably 10 to 30% by mass, and still more preferably 15 to 25% by mass with respect to the total mass of the ink composition.
  • the polymerization initiator is preferably at least one water-soluble polymerization initiator.
  • water-soluble means to dissolve 0.5% by mass or more in distilled water at 25 ° C.
  • the water-soluble polymerization initiator is preferably dissolved at 1% by mass or more in distilled water at 25 ° C., more preferably at least 3% by mass.
  • water-soluble polymerization initiator examples include compounds represented by the following general formula (1), compounds described in JP-A-2005-307198, and the like. Of these, a water-soluble polymerization initiator represented by the following general formula (1) is preferable from the viewpoints of adhesion to a recording medium and abrasion resistance.
  • n and n each independently represents an integer of 0 or more, and m + n represents an integer of 0 to 3. It is preferable that m is 0 to 3 and n is 0 or 1, and it is more preferable that m is 0 or 1 and n is 0. Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.
  • the compound represented by the general formula (1) may be a newly synthesized compound or a commercially available compound.
  • the content of the polymerization initiator with respect to the total mass of the ink composition is preferably in the range of 0.1 to 30% by mass, more preferably in the range of 0.5 to 20% by mass, and 1.0%. It is more preferably in the range of ⁇ 15% by mass, most preferably in the range of 1.0 to 7.0% by mass.
  • Water-soluble organic solvent In the mixing step, it is preferable that at least one water-soluble organic solvent is further subjected to mixing.
  • a water-soluble organic solvent in the black ink composition, it is possible to obtain an effect of preventing drying, wetting or promoting penetration.
  • the water-soluble organic solvent can function as an anti-drying agent that prevents the ink from adhering and drying to form aggregates at the ink discharge port of the ejection nozzle, thereby preventing clogging.
  • a water-soluble organic solvent having a vapor pressure lower than that of water is preferable.
  • the water-soluble organic solvent can function as a penetration enhancer that enhances ink permeability to paper.
  • water-soluble organic solvents examples include alkanediols (polyhydric alcohols) such as glycerin, ethylene glycol, and propylene glycol; sugar alcohols; alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, and isopropanol
  • alkanediols polyhydric alcohols
  • sugar alcohols alkyl alcohols having 1 to 4 carbon atoms
  • alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, and isopropanol
  • Ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propy
  • the mixing step further includes subjecting at least one surfactant to further mixing.
  • the surfactant can be used as a surface tension adjusting agent.
  • As the surface tension modifier a compound having a structure having both a hydrophilic part and a hydrophobic part in the molecule can be used effectively.
  • Anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic properties Either a surfactant or a betaine surfactant can be used.
  • a nonionic surfactant is preferable from the viewpoint of suppression of droplet ejection interference of the ink composition, and an acetylene glycol surfactant is more preferable.
  • acetylene glycol surfactant examples include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne-4,7.
  • -Alkylene oxide adducts of diols can be mentioned, and at least one selected from these is preferable.
  • Examples of commercially available products of these compounds include E series such as Olphine E1010 (product names) manufactured by Nissin Chemical Industry Co., Ltd.
  • the surfactant content is determined from the surface tension of the ink composition from the viewpoint of favorably discharging the ink composition by an ink jet method.
  • the amount is preferably in the range of 20 to 60 mN / m, more preferably 20 to 45 mN / m, and further preferably 25 to 40 mN / m from the viewpoint of surface tension.
  • the specific amount of the surfactant in the black ink composition of the surfactant is not particularly limited except that the surface tension is preferably within a range, and is preferably 0.1% by mass or more, more preferably 0. 0.1 to 10% by mass, more preferably 0.2 to 3% by mass.
  • the method for producing a black ink composition of the present invention preferably includes a step of further mixing at least one colloidal silica.
  • the step of mixing colloidal silica may be performed simultaneously with the mixing step or may be performed independently of the mixing step.
  • the black ink composition contains colloidal silica
  • the effect can be recognized particularly when silicon is used in at least a part of the ink jet head member.
  • the ink composition contains colloidal silica
  • the hydrolysis of the ink component is effectively suppressed, and the stability of the ink composition is improved, so that the ejection of the ink composition on the ink jet recording apparatus is stopped and fixed. It is presumed that even when the ink is left for a period of time and then the discharge is restarted, excellent discharge stability (stand-by recovery performance) can be obtained, and at the same time, the rub resistance of the image can be achieved.
  • colloidal silica is moderately adsorbed on the surface of the ink jet head member to reduce the erosion of the ink jet head member surface by the ink component, thereby preventing the liquid repellency of the ink jet head member from being lowered.
  • Colloidal silica is a colloid composed of inorganic oxide fine particles having an average particle size of several hundred nm or less and containing silicon. Silicon dioxide (including hydrates thereof) may be included as a main component, and aluminate may be included as a minor component. Examples of the aluminate that may be contained as a minor component include sodium aluminate and potassium aluminate.
  • colloidal silica may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium hydroxide. These inorganic salts and organic salts act, for example, as colloid stabilizers.
  • the colloidal silica dispersion medium is not particularly limited and may be water, an organic solvent, or a mixture thereof.
  • the organic solvent may be a water-soluble organic solvent or a water-insoluble organic solvent, but is preferably a water-soluble organic solvent. Specific examples include methanol, ethanol, isopropyl alcohol, n-propanol and the like.
  • colloidal silica is not particularly limited, and can be produced by a commonly used method.
  • it can be produced from aerosil synthesis by thermal decomposition of silicon tetrachloride or water glass.
  • it can also be produced by a liquid phase synthesis method such as hydrolysis of alkoxide (for example, see “Fiber and Industry”, Vol. 60, No. 7 (2004) P376).
  • the average particle size of the particles contained in the colloidal silica is not particularly limited, but is typically 1 nm to 25 nm, preferably 3 nm to 25 nm, more preferably 3 nm to 20 nm, and further preferably 3 nm to 15 nm. Particularly preferred is 5 nm to 10 nm.
  • damage for example, decrease in liquid repellency
  • members constituting the inkjet head such as a base material, a protective film, a liquid repellent film, and the like is more effectively performed. Can be suppressed.
  • the average particle diameter of the particles being 25 nm or less may be suitable from the viewpoint of the dischargeability of the ink composition and the abrasive effect of the particles.
  • productivity can improve that an average particle diameter is 1 nm or more, and colloidal silica with few dispersion
  • the average particle size of the colloidal silica particles can be measured by a method such as a light scattering method or a laser diffraction method, which is a general measurement of dispersed particles.
  • a TEM transmission electron microscope
  • the particle diameters of 300 colloidal silica particles were measured by the photographing method, and the average value was taken as the average particle diameter.
  • the shape of the colloidal silica particles is not particularly limited as long as it does not hinder the ejection performance of the ink composition. For example, any of a spherical shape, a long shape, a needle shape, and a bead shape may be used. Among them, the spherical shape is preferable from the viewpoint of ink ejection.
  • the colloidal silica may be produced by the above production method or may be a commercially available product.
  • Commercially available products include, for example, Ludox AM, Ludox AS, Ludox LS, Ludox TM, Ludox HS, etc. (all registered trademarks, manufactured by EI Du Pont de Nemours &Co); SNOWTEX S, SNOWTEX XS , Snowtex 20, Snowtex 30, Snowtex 40, Snowtex N, Snowtex C, Snowtex O, etc. (all registered trademarks, manufactured by Nissan Chemical Co., Ltd.); Syton C-30, Symantec ZOO, etc.
  • colloidal silica examples include SNOWTEX ST-UP, SNOWTEX PS-S, SNOWTEX PS-M, SNOWTEX ST-OUP, SNOWTEX PS-SO, and SNOWTEX PS.
  • -MO manufactured by Nissan Chemical Co., Ltd.
  • the pH of the above commercially available colloidal silica dispersion is often adjusted to be acidic or alkaline. This is because the stable dispersion region of colloidal silica exists on the acidic side or alkaline side.
  • a commercially available colloidal silica dispersion is added to the ink composition, it must be added in consideration of the pH of the stable dispersion region of the colloidal silica and the pH of the ink composition.
  • the colloidal silica content in the ink composition is not particularly limited, but is preferably 0.005% by mass to 0.5% by mass of the total amount of the ink composition, and more preferably 0.005% of the total amount of the ink composition. It is preferably from 0.01% by weight to 0.1% by weight, particularly preferably from 0.01% by weight to 0.1% by weight of the total amount of the ink composition.
  • the content in the ink composition is not more than the above upper limit value, the dischargeability of the ink composition can be further improved, and the influence on the ink jet head due to the abrasive effect of the silica particles can be more effectively suppressed. .
  • the fall of the liquid repellency of an inkjet head member can be suppressed more effectively because it is more than the said lower limit.
  • the ink composition is made of colloidal silica having an average particle size (TEM imaging method) of 3 nm to 25 nm from the viewpoint of suppressing the decrease in liquid repellency of an ink jet head member and good ink ejection properties.
  • the total amount is preferably 0.005% to 0.5% by mass, and the colloidal silica having an average particle size of 3 nm to 15 nm is preferably included in the total amount of the ink composition from 0.005% to 0.1% by mass. More preferred.
  • the content ratio of colloidal silica to the polymerizable compound (colloidal silica / polymerizable compound) in the ink composition is preferably 0.0001 to 0.1, and preferably 0.001 to 0.05 on a mass basis. It is more preferable.
  • the content ratio of colloidal silica with respect to the polymerizable compound is 0.0001 or more, a decrease in liquid repellency of the inkjet head member can be more effectively suppressed.
  • discharge property can improve more because it is 0.1 or less.
  • the black ink composition may contain resin particles as necessary.
  • the resin particles may be subjected to mixing at the same time in the mixing step, or may be contained in the ink composition by being subjected to mixing independently of the mixing step.
  • the resin particles fix the ink composition by increasing the viscosity of the ink by aggregation or dispersion instability when contacted with the treatment liquid or the region on the dried recording medium after the treatment liquid is applied. It is preferable to have a function (that is, fix an image).
  • the resin particles are preferably used in a form dispersed in at least one of water and an organic solvent.
  • Resin particles include acrylic resins, vinyl acetate resins, styrene-butadiene resins, vinyl chloride resins, acrylic-styrene resins, butadiene resins, styrene resins, crosslinked acrylic resins, crosslinked styrene resins, and benzoguanamine resins.
  • a phenol resin, a silicone resin, an epoxy resin, a urethane resin, a paraffin resin, a fluorine resin, or a latex thereof can be used.
  • Preferred examples include acrylic resins, acrylic-styrene resins, styrene resins, cross-linked acrylic resins, and cross-linked styrene resins.
  • the resin particles can also be used in the form of latex.
  • the weight average molecular weight of the resin particles is preferably 10,000 or more and 200,000 or less, more preferably 20,000 or more and 200,000 or less.
  • the average particle size of the resin particles is preferably in the range of 1 nm to 1 ⁇ m, more preferably in the range of 1 nm to 200 nm, still more preferably in the range of 1 nm to 100 nm, and particularly preferably in the range of 1 nm to 50 nm.
  • the glass transition temperature Tg of the resin particles is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 50 ° C. or higher.
  • the content of the resin particles with respect to the total mass of the black ink composition is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, and further preferably 0.1 to 5% by mass.
  • the particle size distribution of the resin fine particles is not particularly limited, and may be any having a wide particle size distribution or a monodispersed particle size distribution. Resin particles having a monodispersed particle size distribution may be used alone or in combination of two or more.
  • the black ink composition may further contain various additives as other components, if necessary, in addition to the above components.
  • Various additives may be used for mixing at the same time in the mixing step, or may be contained in the ink composition by being used for mixing independently of the mixing step.
  • the various additives include, for example, ultraviolet absorbers, antifading agents, antifungal agents, pH adjusters, rust inhibitors, antioxidants, emulsion stabilizers, preservatives, antifoaming agents, viscosity modifiers, and dispersions.
  • Known additives such as stabilizers or chelating agents can be used.
  • the content of these additives may be appropriately determined according to the application, but may be, for example, about 0.02 to 1.00% by mass with respect to the total mass of the black ink composition.
  • UV absorbers examples include benzophenone UV absorbers, benzotriazole UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, nickel complex salt UV absorbers, and the like.
  • organic and metal complex anti-fading agents can be used as the anti-fading agent.
  • organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, and metal complexes.
  • nickel complex, zinc complex and the like there are nickel complex, zinc complex and the like.
  • antifungal agent examples include, for example, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one, sodium sorbate, pentachlorophenol Sodium etc. are mentioned.
  • the pH adjuster is not particularly limited as long as it can adjust the pH to a desired value without adversely affecting the ink composition to be prepared, and can be appropriately selected according to the purpose.
  • alcohol amines eg, diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol
  • alkali metal hydroxides eg, lithium hydroxide, sodium hydroxide, potassium hydroxide) Etc.
  • ammonium hydroxide for example, ammonium hydroxide, quaternary ammonium hydroxide, etc.
  • phosphonium hydroxide alkali metal carbonate and the like.
  • rust preventive examples include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.
  • antioxidants examples include phenolic antioxidants (including hindered phenolic antioxidants), amine antioxidants, sulfur antioxidants, phosphorus antioxidants, and the like.
  • chelating agent examples include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate and the like.
  • the surface tension (25 ° C.) of the ink composition 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 25 mN / m or more and 40 mN / m or less.
  • the surface tension is measured using an Automatic Surface Tensiometer CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.) under the condition of 25 ° C.
  • the viscosity of the ink composition at 25 ° C. is preferably 1.2 mPa ⁇ s or more and 15.0 mPa ⁇ s or less, more preferably 2 mPa ⁇ s or more and less than 13 mPa ⁇ s, and still more preferably 2 It is not less than 5 mPa ⁇ s and less than 10 mPa ⁇ s.
  • the viscosity is measured using a VISCOMETER TV-22 (trade name, manufactured by TOKI SANGYO CO. LTD) under conditions of 25 ° C. of the ink composition.
  • an aggregate can be formed by applying the black ink composition on a recording medium by an ink jet method and contacting the ink composition. Including applying a treatment liquid containing an aggregating agent on the recording medium, and irradiating the ink composition applied on the recording medium with an active energy ray to cure the ink image, and others as necessary An image forming method that can include these steps can be given.
  • the black ink composition is applied onto a recording medium by an ink jet method.
  • the ink composition can be selectively applied onto the recording medium, and a desired image can be formed.
  • the inkjet method is not particularly limited, and is a known method, for example, a charge control method that discharges ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses vibration pressure of a piezoelectric element, an electric method
  • a charge control method that discharges ink using electrostatic attraction
  • a drop-on-demand method that uses vibration pressure of a piezoelectric element
  • An acoustic ink jet system that converts a signal into an acoustic beam, irradiates the ink with ink and ejects the ink using radiation pressure
  • a thermal ink jet bubble jet (registered trademark)) that heats the ink to form bubbles and uses the generated pressure. )
  • Any method may be used.
  • ink jet method a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving the image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent ink are used. The method is included.
  • An ink jet head used in the ink jet method may be an on-demand method or a continuous method.
  • Discharge methods include electro-mechanical conversion methods (eg, single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.), electro-thermal conversion methods (eg, thermal ink jet type) Specific examples include, for example, bubble jet (registered trademark) type, electrostatic attraction type (eg, electric field control type, slit jet type), and discharge type (eg, spark jet type). Any discharge method may be used.
  • the ink nozzles used when recording by the inkjet method There are no particular restrictions on the ink nozzles used when recording by the inkjet method, and they can be appropriately selected according to the purpose.
  • a short serial head is used, and a recording method is arranged in correspondence with a shuttle method in which recording is performed while the head is scanned in the width direction of the recording medium, and the entire area of one side of the recording medium.
  • an image can be recorded on the entire surface of the recording medium by scanning the recording medium in a direction orthogonal to the arrangement direction of the recording elements, and a carriage system such as a carriage for scanning a short head is not necessary.
  • the recording speed can be increased as compared with the shuttle system.
  • the ink jet recording method can be applied to any of these, but generally, when applied to a line system that does not use a dummy jet, the effect of improving ejection accuracy and image scratch resistance can be increased.
  • the amount of ink droplets ejected from the inkjet head is preferably 0.5 to 6 pl (picoliter), more preferably 1 to 5 pl, and still more preferably 2 to 4 pl from the viewpoint of obtaining a high-definition image.
  • a treatment liquid containing an aggregating agent capable of forming an aggregate by contact with the ink composition is applied to the recording medium, and the treatment liquid is contacted with the ink composition to form an image.
  • the treatment liquid comes into contact with the ink composition, dispersed particles such as resin particles and pigment in the ink composition are aggregated, and the image is fixed on the recording medium. Details and preferred embodiments of each component in the treatment liquid will be described later.
  • the treatment liquid can be applied by applying a known method such as a coating method, an inkjet method, or an immersion method.
  • a coating method include known coating methods using a bar coater, an extrusion die coater, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, and the like.
  • the details of the inkjet method are as described above.
  • the treatment liquid may be applied either before or after the ink composition is applied to the recording medium.
  • a mode in which the ink is applied onto the recording medium after the treatment liquid is applied onto the recording medium in the treatment liquid applying step is preferable. That is, before applying (discharging) the ink composition to the recording medium by the ink jet method, a processing liquid capable of aggregating the pigment in the ink composition is applied in advance, and the processing liquid applied on the recording medium is applied.
  • An embodiment in which an image is formed by discharging the ink composition so as to come into contact with the ink is preferable. Thereby, inkjet recording can be speeded up, and an image with high density and resolution can be obtained even at high speed recording.
  • the amount of treatment liquid applied is not particularly limited as long as the ink composition can be agglomerated, but it can be preferably an amount such that the amount of aggregating agent applied is 0.1 g / m 2 or more.
  • the amount of the flocculant applied is preferably 0.1 to 1.0 g / m 2 , more preferably 0.2 to 0.8 g / m 2 .
  • the amount of the aggregating component applied is 0.1 g / m 2 or more, the aggregating reaction can proceed satisfactorily, and when it is 1.0 g / m 2 or less, the glossiness can be suppressed from becoming too high.
  • the treatment liquid contains at least one aggregating agent capable of forming an aggregate by contact with the black ink composition.
  • the treatment liquid may or may not contain other components as required.
  • the flocculant is capable of aggregating (fixing) components in the ink composition by contacting the ink composition on the recording medium, and functions as a fixing agent, for example.
  • a fixing agent for example, by applying the treatment liquid to a recording medium (preferably coated paper), the ink composition is further deposited on the recording medium in a state where the aggregating agent is present on the recording medium, By contacting, the components in the ink composition can be aggregated, and the ink composition components can be fixed on the recording medium.
  • the flocculant include acidic compounds, polyvalent metal salts, and cationic polymers. Among these, an acidic compound is preferable from the viewpoint of improving the cohesiveness of the ink composition component.
  • a flocculant may be used individually by 1 type, or may use 2 or more types together.
  • acidic compounds include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, and tartaric acid. , Lactic acid, sulfonic acid, orthophosphoric acid, metaphosphoric acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, and derivatives of these compounds, etc. Preferably mentioned.
  • acidic compounds with high water solubility are preferable.
  • a trivalent or less acidic compound is preferable, and a divalent or trivalent acidic compound is particularly preferable.
  • An acidic compound may be used individually by 1 type, and may use 2 or more types together.
  • the pH (25 ° C.) of the treatment liquid is preferably 0.1 to 6.8, more preferably 0.5 to 6.0, and 0.8 More preferably, it is -5.0.
  • the content of the acidic compound is preferably 40% by mass or less, more preferably 15 to 40% by mass, and more preferably 15 to 35% by mass with respect to the total mass of the treatment liquid. Further preferred. By setting the content of the acidic compound to 40% by mass or less, the components in the ink composition can be more efficiently fixed.
  • the treatment liquid preferably contains at least one water-soluble organic solvent in addition to the flocculant.
  • the details of the water-soluble organic solvent are the same as those in the ink composition, and the preferred embodiments are also the same.
  • the treatment liquid may or may not contain other additives as other components as long as the effects of the present invention are not impaired.
  • additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, UV absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, anti-foaming agents.
  • Well-known additives such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned.
  • ink is applied after the treatment liquid is applied, and the treatment liquid on the recording medium is heated and dried after the treatment liquid is applied on the recording medium and before the ink composition is applied. It is preferable. By heating and drying the treatment liquid in advance before the ink application step, ink colorability such as bleeding prevention is improved, and a visible image with good color density and hue can be recorded.
  • Heat drying can be performed by a known heating means such as a heater, a blowing means using blowing air such as a dryer, or a combination of these.
  • a heating method for example, a method of applying heat with a heater or the like from the side opposite to the treatment liquid application surface of the recording medium, a method of applying warm air or hot air to the treatment liquid application surface of the recording medium, an infrared heater was used.
  • the heating method etc. are mentioned, One of these may be used or you may heat combining a plurality.
  • the image forming method preferably removes at least a part of the solvent in the ink composition by heating the ink image formed by applying the ink composition onto a recording medium after the ink ejection.
  • heat-drying treatment it is possible to form an image having better adhesion to a recording medium and an abrasion resistance of an image formed by a subsequent curing step.
  • the method of heating is not particularly limited, but a non-contact drying method such as a method of heating with a heating element such as a nichrome wire heater, a method of supplying warm air or hot air, a method of heating with a halogen lamp, an infrared lamp, etc. Preferably, it can be mentioned.
  • the image forming method preferably includes irradiating the ink composition applied on the recording medium with an active energy ray and curing.
  • the curing step of irradiating the active energy ray is a step of irradiating the ink image formed by applying the ink composition with, for example, ultraviolet rays from an ultraviolet irradiation lamp.
  • the monomer component (water-soluble polymerizable compound) in the image can be surely polymerized and cured.
  • the ultraviolet irradiation lamp is disposed opposite the recording surface of the recording medium and the entire recording surface is irradiated, the entire image can be cured.
  • the light source for irradiating the active energy ray is not limited to the ultraviolet irradiation lamp, but a halogen lamp, a high-pressure mercury lamp, a laser, an LED, an electron beam irradiation apparatus, or the like can also be adopted.
  • the curing step of irradiating the active energy ray may be placed before or after the heat drying as long as it is after ink application and treatment liquid application, and may be performed both before and after the heat drying.
  • the irradiation condition of the active energy ray is not particularly limited as long as the polymerizable compound can be polymerized and cured.
  • the wavelength of the active energy ray is preferably, for example, 200 to 600 nm, more preferably 300 to 450 nm, and further preferably 350 to 420 nm.
  • the output of the active energy ray is preferably at 5000 mJ / cm 2 or less, more preferably 10 ⁇ 4000mJ / cm 2, further preferably 20 ⁇ 3000mJ / cm 2.
  • the image forming method of the present invention records an image on a recording medium.
  • the recording medium is not particularly limited, and general printing paper mainly composed of cellulose, such as so-called high-quality paper, coated paper, and art paper, used for general offset printing and the like can be used.
  • General printing paper mainly composed of cellulose is relatively slow in ink absorption and drying in image recording by a general ink jet method using water-based ink, and color material movement is likely to occur after droplet ejection, and image quality is likely to deteriorate.
  • the image forming method using the ink set the movement of the color material can be suppressed, and a high-quality image excellent in color density and hue can be recorded.
  • the recording medium commercially available media can be used.
  • Fine paper (A) such as “New NPI Fine” manufactured by Oji Paper Co., Ltd., “OK Everlight Coat” manufactured by Oji Paper Co., Ltd., and “Aurora S” manufactured by Nippon Paper Industries Co., Ltd., Oji Paper Co., Ltd.
  • Lightweight coated paper (A3) such as “OK Coat L” manufactured by Nippon Paper Industries Co., Ltd. and “Aurora L” manufactured by Nippon Paper Industries Co., Ltd.
  • the water absorption coefficient Ka of the recording medium is preferably 0.05 to 0 from the viewpoint that the effect of suppressing the movement of the coloring material is large and that a high-quality image with better color density and hue than before can be obtained. .5 in a mL / m 2 ⁇ ms 1/2, more preferably 0.1 ⁇ 0.4mL / m 2 ⁇ ms 1/2, more preferably 0.2 ⁇ 0.3mL / m 2 ⁇ ms 1/2 .
  • the water absorption coefficient Ka is synonymous with that described in JAPANJTAPPI paper pulp test method No 51: 2000 (issued by Japan Paper Pulp Technology Association).
  • the absorption coefficient Ka is an automatic scanning absorption meter. It is calculated from the difference in the amount of water transferred between the contact time of 100 ms and the contact time of 900 ms using KM500Win (manufactured by Kumagai Riki Co., Ltd.).
  • coated paper used for general offset printing is preferable.
  • the coated paper is obtained by applying a coating material to the surface of high-quality paper, neutral paper, or the like that is mainly surface-treated with cellulose as a main component and is not generally surface-treated.
  • the coated paper tends to cause quality problems such as image gloss and scratch resistance in image formation by a normal aqueous inkjet, but the inkjet recording method can suppress gloss unevenness, gloss and abrasion resistance.
  • An image with good properties can be obtained.
  • the composition of the obtained water-insoluble resin P-1 was confirmed by 1 H-NMR, and the weight average molecular weight (Mw) determined by GPC was 49400. Furthermore, when the acid value of this water-insoluble resin was determined by the method described in JIS standard (JIS K 0070: 1992), it was 84.8 mgKOH / g.
  • a high-speed cooling centrifuge 7550 (trade name, manufactured by Kubota Seisakusho) was used to centrifuge at a capacity of 50 mL. Centrifugal treatment was performed at 8000 rpm for 30 minutes using a spear, and the supernatant liquid other than the precipitate was collected. Thereafter, the pigment concentration was determined from the absorbance spectrum, and ion-exchanged water was added to obtain a carbon black pigment aqueous dispersion CB1 as a dispersion of resin-coated pigment particles (encapsulated pigment) having a pigment concentration of 15% by mass.
  • Pigment Dispersion 2 was obtained as follows. 13.6 parts of carbon black pigment, 6.2 parts of the dispersant P-2, 9.3 parts of 1 mol / L NaOH aqueous solution, and 70.9 parts of ion-exchanged water were mixed, and 0. Dispersion was performed for 3 hours using 1 mm ⁇ zirconia beads. Thereafter, 0.87 part of trimethylolpropane triglycidyl ether and 0.38 part of boric acid were added and reacted at 60 ° C. for 6 hours, followed by cooling. Further, a high-speed cooling centrifuge 7550 (trade name, manufactured by Kubota Corporation) was used.
  • aqueous carbon black pigment dispersion CB2 as a dispersion of resin-coated pigment particles having a carbon black concentration of 13% by mass. It was 92 nm when the volume average particle diameter was measured by the method similar to the above.
  • the pigment concentration was determined from the absorbance spectrum, and ion exchange water was added to obtain an aqueous carbon black pigment dispersion CB3 having a carbon black concentration of 10.0% by mass.
  • the volume average particle size was measured by the same method as described above, it was 90 nm.
  • a colored pigment aqueous dispersion C1 was obtained in the same manner as described above except that in the preparation of the aqueous carbon black pigment dispersion 1, Pigment Blue 15: 3 was used instead of the carbon black pigment. It was 93 nm when the volume average particle diameter was measured by the method similar to the above.
  • a colored pigment aqueous dispersion M1 was obtained in the same manner as described above except that in the preparation of the colored pigment dispersion C1, Pigment Red 122 was used instead of Pigment Blue 15: 3. It was 78 nm when the volume average particle diameter was measured by the method similar to the above.
  • Colored pigment aqueous dispersion Y1 was obtained in the same manner as described above except that in the preparation of Pigment Dispersion 1, Pigment Yellow 74 was used instead of Pigment Blue 15: 3. It was 95 nm when the volume average particle diameter was measured by the method similar to the above.
  • the aqueous layer was extracted four times with 200 ml of ethyl acetate, and the obtained organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain 35.0 g of the target polymerizable compound 2 solid. (107 mmol, 59% yield).
  • Example 1> Carbon black pigment aqueous dispersion CB1 obtained above, colored pigment aqueous dispersion C1, polymerizable compound 2, colloidal silica (Snowtex XS (registered trademark), average particle size 5 nm, Nissan Chemical Industries, Ltd. Each component was mixed so as to have the following ink composition. This was packed in a plastic disposable syringe and filtered through a PVDF 5 ⁇ m filter (Millex-SV (registered trademark), diameter 25 mm, manufactured by Millipore) to prepare a black ink composition Bk-1.
  • PVDF 5 ⁇ m filter Millex-SV (registered trademark), diameter 25 mm, manufactured by Millipore
  • Example 2 the black ink composition Bk was used in the same manner as in Example 1 except that the types and addition amounts of the carbon black pigment aqueous dispersion and the colored pigment aqueous dispersion were changed so as to have the formulation shown in Table 1. -2 to 6 were prepared respectively. In Table 1, the addition amounts of the carbon black pigment and the color pigment each mean solid mass.
  • Example 7 A black ink composition Bk-7 was prepared in the same manner as in Example 4 except that the polymerizable compound 5 was used in place of the polymerizable compound 2 in Example 4.
  • Example 8 the black ink composition Bk-8 was prepared in the same manner as in Example 4 except that Zonyl FSN (registered trademark, manufactured by DuPont) was used instead of the surfactant Olfine E1010 (described above). Prepared.
  • Zonyl FSN registered trademark, manufactured by DuPont
  • Example 1 the black ink composition Bk-9 was prepared in the same manner as in Example 1 except that the addition amount of the carbon black pigment aqueous dispersion CB1 was changed to 20% without using the color pigment aqueous dispersion. Prepared.
  • the component of the following composition was mixed and the processing liquid 1 was prepared.
  • the treatment liquid 1 had a viscosity of 2.5 mPa ⁇ s, a surface tension of 40 mN / m, and a pH of 1.0 at 25 ° C.
  • the surface tension is measured using a fully automatic surface tension meter CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.), and the viscosity is measured using DV-III Ultra CP (trade name, manufactured by Brookfield Engineering). did.
  • the pH was measured using a PH meter HM-30R (trade name, manufactured by Toa DKK Corporation).
  • An ink jet head provided with a silicon nozzle plate was prepared, and the black ink composition obtained above was refilled in a storage tank connected thereto.
  • the silicon nozzle plate is previously provided with a liquid repellent film using a fluorinated alkylsilane compound.
  • “OK Top Coat +” (trade name, manufactured by Oji Paper Co., Ltd., basis weight 104.7 g / m 2 ) as a recording medium is cut into A5 size and on a stage that can move in a predetermined linear direction at 500 mm / sec. The stage temperature was kept at 30 ° C.
  • the treatment liquid 1 obtained above was applied to this with a bar coater so as to have a thickness of about 1.2 ⁇ m, and was dried at 50 ° C. for 2 seconds immediately after the application. Thereafter, the inkjet head is fixedly arranged so that the direction of the line head in which the nozzles are arranged (main scanning direction) is inclined by 75.7 degrees with respect to the direction orthogonal to the moving direction of the stage (sub-scanning direction), and recording is performed.
  • a solid image is obtained by ejecting ink over the entire surface of the recording medium in a line system under the ejection conditions of an ink droplet amount of 2.8 pL, an ejection frequency of 25.5 kHz, a resolution of 1200 dpi ⁇ 1200 dpi while moving the medium at a constant speed in the sub-scanning direction Formed. After the image was recorded, while being heated with an infrared heater from the back side (back side) of the ink landing surface, warm air of 120 ° C. and 5 m / sec was applied to the recording surface for 15 seconds and dried.
  • UV light was irradiated from a metal halide lamp (manufactured by Eye Graphics Co., Ltd., maximum irradiation wavelength 365 nm) so as to obtain an integrated irradiation amount of 3 J / cm 2 , and the image was cured to obtain a print sample.
  • a metal halide lamp manufactured by Eye Graphics Co., Ltd., maximum irradiation wavelength 365 nm
  • the obtained print sample was visually observed to confirm that ink was ejected from all nozzles. After this line image is formed, the head is left as it is for a predetermined time, and then a new recording medium is attached to the stage, and ink is discharged again under the same conditions as above to print a print sample (line image). Produced.
  • the obtained print sample (line image) was visually observed, and after standing for a predetermined time, 2000 ink droplets were ejected, and the standing restorability was evaluated using the maximum standing time during which all 96 nozzles could be ejected as an index. . The longer the standing time during which no ejection failure occurred, the better the ejection performance, and the evaluation was based on the following evaluation criteria. The evaluation results are shown in Table 1.
  • a method for producing a black ink composition for ink jet recording capable of forming an image which can be excellent in ejection stability and can be excellent in adhesion to a recording medium.

Abstract

La présente invention concerne un procédé de production d'une composition d'encre noire pour impression jet d'encre, comprenant les étapes consistant à préparer une dispersion aqueuse d'un pigment à base de noir de carbone contenant un pigment de type noir de carbone en tant que pigment; à préparer une dispersion aqueuse d'un pigment coloré contenant au moins un pigment coloré choisi dans le groupe constitué d'un pigment magenta, d'un pigment cyan et d'un pigment jaune en tant que pigment; et à mélanger ensemble la dispersion aqueuse du pigment à base de noir de carbone, la dispersion aqueuse du pigment coloré, un composé polymérisable soluble dans l'eau et un initiateur de polymérisation.
PCT/JP2011/073857 2010-10-29 2011-10-17 Procédé de production d'une composition d'encre noire WO2012056932A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-243482 2010-10-29
JP2010243482A JP2012097143A (ja) 2010-10-29 2010-10-29 黒色系インク組成物の製造方法

Publications (1)

Publication Number Publication Date
WO2012056932A1 true WO2012056932A1 (fr) 2012-05-03

Family

ID=45993646

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/073857 WO2012056932A1 (fr) 2010-10-29 2011-10-17 Procédé de production d'une composition d'encre noire

Country Status (2)

Country Link
JP (1) JP2012097143A (fr)
WO (1) WO2012056932A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7333217B2 (ja) * 2019-07-03 2023-08-24 花王株式会社 インクセット

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10130558A (ja) * 1996-09-03 1998-05-19 Fujitsu Isotec Ltd 水性顔料系インク及びインクジェットプリンタ
JPH10287035A (ja) * 1997-04-16 1998-10-27 Seiko Epson Corp インクジェット記録方法、記録物及びインクジェット記録装置
JPH11228886A (ja) * 1998-02-09 1999-08-24 Seiko Epson Corp 黒色再現性に優れたブラックインク
JP2000186242A (ja) * 1998-04-28 2000-07-04 Canon Inc インク、それを用いるインクジェット記録方法及び光重合開始剤
JP2005320541A (ja) * 2004-05-06 2005-11-17 Agfa Gevaert Nv 放射線−硬化可能なインキ−ジェット印刷
JP2007217508A (ja) * 2006-02-15 2007-08-30 Canon Inc インクジェット用インク、インクジェット記録方法、インクカートリッジ、記録ユニット及びインクジェット記録装置
JP2009144007A (ja) * 2007-12-12 2009-07-02 Kao Corp インクジェット記録用水系インク
JP2009190379A (ja) * 2008-02-18 2009-08-27 Fujifilm Corp インク組成物、インクセット、及び画像形成方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10130558A (ja) * 1996-09-03 1998-05-19 Fujitsu Isotec Ltd 水性顔料系インク及びインクジェットプリンタ
JPH10287035A (ja) * 1997-04-16 1998-10-27 Seiko Epson Corp インクジェット記録方法、記録物及びインクジェット記録装置
JPH11228886A (ja) * 1998-02-09 1999-08-24 Seiko Epson Corp 黒色再現性に優れたブラックインク
JP2000186242A (ja) * 1998-04-28 2000-07-04 Canon Inc インク、それを用いるインクジェット記録方法及び光重合開始剤
JP2005320541A (ja) * 2004-05-06 2005-11-17 Agfa Gevaert Nv 放射線−硬化可能なインキ−ジェット印刷
JP2007217508A (ja) * 2006-02-15 2007-08-30 Canon Inc インクジェット用インク、インクジェット記録方法、インクカートリッジ、記録ユニット及びインクジェット記録装置
JP2009144007A (ja) * 2007-12-12 2009-07-02 Kao Corp インクジェット記録用水系インク
JP2009190379A (ja) * 2008-02-18 2009-08-27 Fujifilm Corp インク組成物、インクセット、及び画像形成方法

Also Published As

Publication number Publication date
JP2012097143A (ja) 2012-05-24

Similar Documents

Publication Publication Date Title
JP5554302B2 (ja) 黒色系インク組成物、インクセット及び画像形成方法
US8757786B2 (en) Ink set and image forming method
JP5611858B2 (ja) インク組成物および画像形成方法
JP5473721B2 (ja) インクジェット用インク組成物およびその製造方法、インクセット、ならびに画像形成方法
JP5694826B2 (ja) 黒色系インク組成物、インクセット及び画像形成方法
JP5575594B2 (ja) インク組成物、インクセットおよび画像形成方法
JP2015067802A (ja) インクジェット記録用インク、インクセット、画像形成方法及びメンテナンス方法
JP5554392B2 (ja) 画像形成方法
JP5734938B2 (ja) 画像形成方法
JP5355464B2 (ja) インク組成物、インクセット、及び画像形成方法
JP2012007071A (ja) インク組成物、インクセット及び画像形成方法。
WO2018180284A1 (fr) Composition d'encre aqueuse pour impression à jet d'encre, procédé de formation d'image et microparticules de résine
US20110229641A1 (en) Ink composition, ink set and image forming method
JP5455818B2 (ja) インク組成物、インクセット及び画像形成方法
JP5570924B2 (ja) インク組成物、インクセットおよび画像形成方法
JP2013185136A (ja) インクセット及び画像形成方法
JP5885968B2 (ja) 黒色系インク組成物、インクセット及び画像形成方法
JP2012097142A (ja) 黒色系インク組成物およびインクセット
WO2012056932A1 (fr) Procédé de production d'une composition d'encre noire
JP2013185135A (ja) インクセット及び画像形成方法
JP2012001632A (ja) インク組成物、インクセット及び画像形成方法
JP2013053173A (ja) インク組成物、インクセット、及び画像形成方法
JP5972623B2 (ja) 光重合開始剤、及びそれを用いたインク組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11836068

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11836068

Country of ref document: EP

Kind code of ref document: A1