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WO2024162297A1 - Composition d'encre, ensemble d'encres, support d'impression et procédé d'impression à jet d'encre - Google Patents

Composition d'encre, ensemble d'encres, support d'impression et procédé d'impression à jet d'encre Download PDF

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Publication number
WO2024162297A1
WO2024162297A1 PCT/JP2024/002750 JP2024002750W WO2024162297A1 WO 2024162297 A1 WO2024162297 A1 WO 2024162297A1 JP 2024002750 W JP2024002750 W JP 2024002750W WO 2024162297 A1 WO2024162297 A1 WO 2024162297A1
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WO
WIPO (PCT)
Prior art keywords
ink composition
mass
less
composition according
acid
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2024/002750
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English (en)
Japanese (ja)
Inventor
径明 武田
勇之介 笠
由昌 宮沢
悠太 萩原
麻衣子 岩見
光佑 多湖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
Original Assignee
Nippon Kayaku Co Ltd
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 Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Priority to JP2024574911A priority Critical patent/JPWO2024162297A1/ja
Publication of WO2024162297A1 publication Critical patent/WO2024162297A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/17—Ink jet characterised by ink handling
    • B41J2/18—Ink recirculation systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/21—Ink jet for multi-colour printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing

Definitions

  • the present invention relates to an ink composition, an ink set, a recording medium, and an inkjet recording method.
  • the printing method using an inkjet printer is a method in which ink is sprayed from a nozzle and deposited on a recording medium. Unlike conventional printing methods, the inkjet printing method does not use plates, and is therefore expected to be used in a wide range of fields as an on-demand printing method that can handle small quantities of a wide variety of products.
  • white ink When printing on a recording medium that is not white, white ink may be used to express the color white. Also, in order to hide the color of the recording medium itself and increase visibility, a white base may be formed using white ink, and then a color image may be formed using color inks.
  • Titanium oxide is known as a white pigment contained in white ink.
  • titanium oxide has a higher specific gravity than organic pigments, and the particle size tends to be relatively large in order to achieve sufficient whiteness.
  • the titanium oxide may settle or aggregate during storage of the ink, which may adversely affect the ejection properties of the ink. If titanium oxide settles or aggregates during storage of the ink, it is necessary to redisperse the ink using a stirrer before installing it in the inkjet printer, but even using a stirrer may not be enough to completely break down the aggregates.
  • titanium oxide may settle or aggregate in the ink flow path, which may adversely affect the ejection properties of the ink.
  • the present invention aims to provide an ink composition that has excellent dispersion stability and inkjet ejection properties of titanium oxide and is capable of producing printed matter with excellent color development, an ink set that includes the ink composition, a recording medium to which the ink composition is applied, and an inkjet recording method that uses the ink composition.
  • ⁇ 1> Contains titanium oxide, a polymer dispersant, and a flocculant,
  • the ink composition has a titanium oxide content of 1% by mass or more and less than 30% by mass.
  • ⁇ 2> The ink composition according to ⁇ 1>, further comprising water.
  • ⁇ 3> The ink composition according to ⁇ 1> or ⁇ 2>, wherein the polymer dispersant has an acid value and/or an amine value that satisfies the formula (acid value)-(amine value) ⁇ 50 mgKOH/g.
  • ⁇ 4> The ink composition according to any one of ⁇ 1> to ⁇ 3>, wherein the amine value of the polymer dispersant is from 0 mgKOH/g to 130 mgKOH/g.
  • ⁇ 5> The ink composition according to any one of ⁇ 1> to ⁇ 4>, wherein the aggregating agent contains a polyvalent metal salt or a cationic resin.
  • the flocculant comprises a polyvalent metal salt,
  • the ink composition according to ⁇ 5>, wherein the content of the polyvalent metal salt is 1% by mass or more and 70% by mass or less with respect to the content of the titanium oxide.
  • the ink composition according to ⁇ 6> wherein the polyvalent metal salt is at least one salt selected from the group consisting of calcium salts and magnesium salts.
  • the flocculant contains a cationic resin having a constituent unit derived from a vinyl monomer having a quaternary ammonium salt group and having a mass average molecular weight of 1,500 or more and 25,000 or less;
  • ⁇ 10> The ink composition according to any one of ⁇ 1> to ⁇ 9>, further comprising an organic solvent.
  • ⁇ 11> ⁇ 10> An ink set comprising the ink composition according to any one of ⁇ 1> to ⁇ 10>, and a white ink composition containing a white colorant and an anionic dispersant.
  • ⁇ 12> ⁇ 10> An ink set comprising the ink composition according to any one of ⁇ 1> to ⁇ 10>, and a non-white ink composition containing a non-white colorant and an anionic dispersant.
  • ⁇ 13> A recording medium to which the ink composition according to any one of ⁇ 1> to ⁇ 10> or each ink composition included in the ink set according to ⁇ 11> or ⁇ 12> is adhered.
  • ⁇ 14> The recording medium according to ⁇ 13>, wherein the recording medium is a permeable recording medium.
  • the permeable recording medium is a liner paper for cardboard.
  • An inkjet recording method comprising ejecting the ink composition according to any one of ⁇ 1> to ⁇ 10> or each ink composition included in the ink set according to ⁇ 11> or ⁇ 12> from an inkjet head and depositing the ink composition on a recording medium.
  • ⁇ 17> The inkjet recording method according to ⁇ 16>, wherein the recording medium is liner paper.
  • ⁇ 18> The inkjet recording method according to ⁇ 16> or ⁇ 17>, wherein the inkjet head has a circulation mechanism.
  • the present invention provides an ink composition that has excellent dispersion stability of titanium oxide and excellent inkjet ejection properties, and is capable of producing printed matter with excellent color development, an ink set that includes the ink composition, a recording medium to which the ink composition is applied, and an inkjet recording method that uses the ink composition.
  • (meth)acrylic acid means both “acrylic acid” and “methacrylic acid”.
  • (meth)acrylate and “(meth)acrylamide”.
  • the ink composition according to the present embodiment contains titanium oxide, a polymeric dispersant, and an aggregating agent, and the content of titanium oxide is 1% by mass or more and less than 30% by mass.
  • the ink composition according to the present embodiment is excellent in dispersion stability of titanium oxide and inkjet dischargeability.
  • an anionic white ink composition to the same area on a recording medium, a printed matter having excellent white color development can be obtained.
  • a printed matter having excellent color development can be obtained.
  • the polymeric dispersant is adsorbed on the surface of the titanium oxide contained in the ink composition according to the present embodiment, thereby narrowing the particle size distribution width of the titanium oxide, and improving the dispersion stability and inkjet dischargeability of the ink composition.
  • the aggregating agent contained in the ink composition according to the present embodiment causes the anionic components contained in the anionic white ink composition or the non-white ink composition to aggregate, thereby reducing the fluidity of the ink and obtaining a printed matter having excellent color development.
  • the ink composition according to the present embodiment contains titanium oxide.
  • the crystal structure of titanium oxide includes rutile type (tetragonal crystal), anatase type (tetragonal crystal), and brookite type (orthorhombic crystal), and from the viewpoints of crystal stability, hiding power, and availability, it is preferable to use rutile type titanium oxide.
  • titanium oxide can be produced by a gas phase method or a liquid phase method, and titanium oxide produced by a gas phase method is preferable because it is easy to obtain titanium oxide with high crystallinity.
  • Titanium oxide has the ability to decompose organic matter due to photocatalytic activity. For this reason, it is preferable to treat the surface of titanium oxide particles with alumina from the viewpoint of sealing the photocatalytic activity and improving the wettability of titanium oxide during dispersion. Furthermore, it is more preferable to treat the surface of titanium oxide particles with alumina and silica from the viewpoint of adjusting the acid-base state of the surface of titanium oxide particles and improving durability. In other words, titanium oxide that has been surface-treated with alumina treatment or alumina-silica treatment is preferable.
  • examples of surface treatment of titanium oxide with inorganic substances include a method of surface treatment by coating with inorganic hydrates containing zinc, magnesium, zirconium, etc. Surface-treated titanium oxide can be fired at 800°C to 1000°C to improve the fluidity and dispersibility of the secondary particle size without promoting sintering between particles.
  • the particle shape of titanium oxide is not particularly limited, and examples include granular and needle-like shapes.
  • the average primary particle diameter of titanium oxide is preferably 100 nm or more, more preferably 150 nm or more, and even more preferably 200 nm or more.
  • the average primary particle diameter of titanium oxide is preferably 600 nm or less, more preferably 500 nm or less, and even more preferably 400 nm or less.
  • the content of titanium oxide in the ink composition according to this embodiment is 1% by mass or more and less than 30% by mass, and from the viewpoint of whiteness and dispersion stability, it is preferably 2% by mass or more and 25% by mass or less, more preferably 5% by mass or more and 20% by mass or less, even more preferably 7% by mass or more and 18% by mass or less, and particularly preferably 8% by mass or more and 16% by mass or less.
  • the ink composition according to this embodiment contains a polymer dispersant.
  • the polymer dispersant is not particularly limited as long as it is a polymer having a mass average molecular weight of 2500 or more that can disperse titanium oxide.
  • the polymer dispersant may have an acid value.
  • the acid value of the polymer dispersant is preferably 0 mgKOH/g or more and 120 mgKOH/g or less, more preferably 0 mgKOH/g or more and 20 mgKOH/g or less, and even more preferably 0 mgKOH/g or more and 10 mgKOH/g or less.
  • the acid value of the polymer dispersant can be calculated in accordance with JIS K0070.
  • the polymer dispersant may have an amine value.
  • the amine value of the polymer dispersant is preferably 0 mgKOH/g or more and 130 mgKOH/g or less, more preferably 10 mgKOH/g or more and 120 mgKOH/g or less, even more preferably 20 mgKOH/g or more and 75 mgKOH/g or less, and particularly preferably 40 mgKOH/g or more and 60 mgKOH/g or less.
  • the amine value of the polymer dispersant can be measured by potentiometric titration in accordance with JIS K7237.
  • the polymer dispersant preferably has an acid value and/or amine value that meets the condition "(acid value) - (amine value) ⁇ 50 mgKOH/g".
  • the value expressed by (acid value) - (amine value) is more preferably 10 mgKOH/g or less, even more preferably -100 mgKOH/g or more and 5 mgKOH/g or less, particularly preferably -80 mgKOH/g or more and 0 mgKOH/g or less, especially preferably -70 mgKOH/g or more and less than -8 mgKOH/g, extremely preferably -60 mgKOH/g or more and less than -30 mgKOH/g, and most preferably -55 mgKOH/g or more and less than -45 mgKOH/g.
  • the titanium oxide content is 2% by mass or more and 25% by mass or less, and the value represented by the (acid value)-(amine value) of the polymer dispersant is 50 mgKOH/g or less, it is more preferable that the titanium oxide content is 2% by mass or more and 5% by mass or less, and the value represented by the (acid value)-(amine value) of the polymer dispersant is 10 mgKOH/g or less, it is even more preferable that the titanium oxide content is 2% by mass or more and 25% by mass or less, and the value represented by the (acid value)-(amine value) of the polymer dispersant is -100 mgKOH/g or more and 5 mgKOH/g or less, it is even more preferable that the titanium oxide content is 5% by mass or more and 20 ....
  • the titanium oxide content is 7% by mass or more and 18% by mass or less, and the value of the polymer dispersant expressed as (acid value)-(amine value) is -70 mgKOH/g or more and less than -8 mgKOH/g, it is extremely preferable that the titanium oxide content is 8% by mass or more and 16% by mass or less, and the value of the polymer dispersant expressed as (acid value)-(amine value) is -60 mgKOH/g or more and less than -30 mgKOH/g, and it is most preferable that the titanium oxide content is 8% by mass or more and 16% by mass or less, and the value of the polymer dispersant expressed as (acid value)-(amine value) is -55 mgKOH/g or more and -45 mgKOH/g or less.
  • Polymer dispersants are available as commercially available products. Examples of commercially available polymer dispersants include the DISPERBYK series manufactured by BYK Japan Co., Ltd. and the Joncryl series manufactured by BASF.
  • the content of the polymer dispersant in the ink composition according to this embodiment is preferably 0.03% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 4% by mass or less, even more preferably 0.15% by mass or more and 3% by mass or less, and particularly preferably 0.2% by mass or more and 2.5% by mass or less.
  • the ink composition according to the present embodiment contains an aggregating agent.
  • the aggregating agent is not particularly limited as long as it can aggregate the anionic components. Examples of the aggregating agent include polyvalent metal salts and cationic resins.
  • the polyvalent metal salt is composed of a divalent or higher polyvalent metal ion and at least one acidic compound selected from an organic acidic compound and an inorganic acidic compound that binds to the polyvalent metal ion, and is soluble in water.
  • the polyvalent metal salt may be one that is generated in the ink composition by adding a hydroxide of the polyvalent metal ion and an organic acidic compound to the ink composition.
  • the polyvalent metal salt may be an anhydrous salt or a hydrate.
  • polyvalent metal ions examples include calcium ions, magnesium ions, aluminum ions, titanium ions, iron (II) ions, iron (III) ions, cobalt ions, nickel ions, copper ions, zinc ions, barium ions, and strontium ions.
  • calcium ions, magnesium ions, nickel ions, zinc ions, and aluminum ions are preferred from the viewpoint of aggregation rate.
  • the organic acidic compound is not particularly limited as long as it is an organic compound having at least one acidic group.
  • the acidic group include a phosphate group, a phosphonic acid group, a phosphinic acid group, a sulfate group, a sulfonic acid group, a sulfinic acid group, and a carboxy group.
  • the phosphate group and the carboxy group are preferred, and the carboxy group is more preferred.
  • organic compounds having a carboxy group examples include polyacrylic acid, acetic acid, glycolic acid, propionic acid, lactic acid (preferably DL-lactic acid), isobutyric acid, L-aspartic acid, gluconic acid, oxalic acid, malonic acid, malic acid (preferably DL-malic acid), maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, phthalic acid, 4-methylphthalic acid, lactic acid, D-isoascorbic acid, itaconic acid, levulinic acid, mandelic acid, 1,4-cyclohexanedicarboxylic acid, tannic acid, 3-ethoxypropionic acid, 2,2-bis(hydroxymethyl)propionic acid, and derivatives thereof.
  • organic carboxylic acid examples include polyacrylic acid, acetic acid, glycolic acid, propionic acid, lactic acid (preferably DL-lactic acid), isobutyric acid, L
  • organic acidic compounds 2,2-bis(hydroxymethyl)propionic acid, 1,4-cyclohexanedicarboxylic acid, L-aspartic acid, and gluconic acid are preferred because of their excellent color development properties, and 2,2-bis(hydroxymethyl)propionic acid and 1,4-cyclohexanedicarboxylic acid are more preferred because of their excellent inkjet ejection properties and storage stability.
  • an organic acid salt generated from a hydroxide of a polyvalent metal ion e.g., calcium hydroxide
  • 2,2-bis(hydroxymethyl)propionic acid, 1,4-cyclohexanedicarboxylic acid, L-aspartic acid, or gluconic acid is preferred.
  • inorganic acidic compounds examples include hydrochloric acid, bromic acid, nitric acid, and sulfuric acid.
  • nitric acid is preferred because it is less corrosive to the metal components that make up the inkjet head and printer.
  • a polyvalent metal salt composed of a polyvalent metal ion and an inorganic acidic compound a nitrate of a polyvalent metal (e.g., calcium) is preferred.
  • the content of the polyvalent metal salt relative to the titanium oxide content is preferably 1% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 50% by mass or less, even more preferably 8% by mass or more and 45% by mass or less, particularly preferably 10% by mass or more and less than 40% by mass, and extremely preferably more than 10% by mass or more and 30% by mass or less.
  • the content of the polyvalent metal salt in the ink composition is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, even more preferably 0.7% by mass or more and 7% by mass or less, particularly preferably 0.9% by mass or more and 6% by mass or less, especially preferably 1.2% by mass or more and less than 6% by mass, extremely preferably 1.5% by mass or more and less than 5% by mass, and most preferably 2% by mass or more and 4% by mass or less.
  • the cationic resin examples include those having a constituent unit derived from a vinyl monomer having a quaternary ammonium salt group and having a mass average molecular weight of from 1500 to 25000. From the viewpoints of the dispersion stability and inkjet dischargeability of titanium oxide, the mass average molecular weight of the cationic resin is preferably from 1500 to 23000, more preferably from 3000 to 22000, and even more preferably from 5000 to 22000.
  • vinyl monomers having a quaternary ammonium base examples include diallyldimethylammonium salt, methacryloyloxyethyltrimethylammonium salt, and methacryloyloxyethyldimethylbenzylammonium salt.
  • the proportion of constituent units derived from vinyl monomers having a quaternary ammonium base in the cationic resin is preferably 30 mol% or more, more preferably 45 mol% or more, and even more preferably 80 mol% or more.
  • the content of the cationic resin relative to the titanium oxide content is preferably 0.5% by mass or more and 18% by mass or less, more preferably 1% by mass or more and 16% by mass or less, even more preferably 2% by mass or more and 14% by mass or less, particularly preferably 3% by mass or more and 12% by mass or less, and extremely preferably 4% by mass or more and 10% by mass or less.
  • the content of the cationic resin in the ink composition is preferably 0.1% by mass or more and 4.5% by mass or less, more preferably 0.15% by mass or more and 3.5% by mass or less, even more preferably 0.2% by mass or more and 3% by mass or less, particularly preferably 0.3% by mass or more and 2.5% by mass or less, especially preferably 0.35% by mass or more and 2% by mass or less, extremely preferably 0.4% by mass or more and 1.8% by mass or less, and most preferably 0.5% by mass or more and 1.5% by mass or less.
  • the ink composition according to this embodiment may contain water.
  • water water containing a small amount of impurities such as metal ions, that is, ion-exchanged water, distilled water, or the like, is preferable.
  • the water content in the ink composition is preferably 55% by mass or more and 90% by mass or less, and more preferably 60% by mass or more and 85% by mass or less.
  • the ink composition according to this embodiment may further contain ink preparation agents in addition to the above-mentioned components, such as a resin emulsion, an organic solvent, a viscosity adjuster, a surfactant, a preservative, an antifungal agent, a pH adjuster, a chelating agent, an antirust agent, a water-soluble ultraviolet absorber, an antioxidant, and an antifoaming agent.
  • ink preparation agents in addition to the above-mentioned components, such as a resin emulsion, an organic solvent, a viscosity adjuster, a surfactant, a preservative, an antifungal agent, a pH adjuster, a chelating agent, an antirust agent, a water-soluble ultraviolet absorber, an antioxidant, and an antifoaming agent.
  • the resin emulsion is different from the above-mentioned polymer dispersant, and preferably has an acid value of less than 50 mgKOH/g.
  • a resin emulsion having an acid value of less than 50 mgKOH/g in the ink composition the viscosity of the ink composition can be adjusted to a suitable range, and there is a tendency that a printed image with extremely little graininess can be realized.
  • the resin emulsion at least one selected from a polymer emulsion and a wax emulsion is preferable.
  • the method for preparing the resin emulsion is not particularly limited. Examples include a method in which the resin is mechanically finely divided in an aqueous medium and dispersed; a method in which the resin emulsion is prepared by emulsion polymerization, dispersion polymerization, suspension polymerization, or the like. Emulsion polymerization can be carried out using an emulsifier or in a soap-free manner.
  • An example of a method for preparing the resin emulsion is the method disclosed in Production Example 1 of JP-A-2000-336292.
  • the resin content of the resin emulsion is preferably 20% by mass or more and 50% by mass or less.
  • polymer emulsions examples include emulsions containing urethane-based, polyester-based, acrylic-based, vinyl acetate-based, vinyl chloride-based, styrene-acrylic-based, acrylic-silicone-based, and styrene-butadiene-based polymers.
  • emulsions of polymers selected from urethane-based, acrylic-based, and styrene-butadiene-based are preferred, with acrylic polymer emulsions being more preferred.
  • polymer emulsions include, for example, urethane-based polymer emulsions such as U-coat UX-320 (acid value: 10 mg KOH/g) manufactured by Sanyo Chemical Industries, Ltd., and WBR-016U (acid value: 7 mg KOH/g) and WBR-2101 (acid value: 10 mg KOH/g) manufactured by Taisei Fine Chemical Co., Ltd.; polyester-based polymer emulsions such as Vylonal MD-1480 (acid value: 3 mg KOH/g), Vylonal MD-1985 (acid value: 2 mg KOH/g), and Vylonal MD-2000 (acid value: 2 mg KOH/g) manufactured by Toyobo Co., Ltd.; vinyl acetate-based polymer emulsions such as Vinyblan 715 (acid value: 8 mg KOH/g) and Vinyblan 985 (acid value: 5 mg KOH/g) manufactured by Nissin Chemical Industry Co., Ltd.; and
  • wax emulsion a water-based wax emulsion is preferred.
  • natural wax and synthetic wax can be used.
  • natural wax for example, petroleum wax such as paraffin wax and microcrystalline wax; lignite wax such as montan wax; vegetable wax such as carnauba wax and candelilla wax; animal and vegetable wax such as beeswax and lanolin; etc. are listed.
  • synthetic wax for example, polyalkylene wax (preferably poly C2-C4 alkylene wax), oxidized polyalkylene wax (preferably poly C2-C4 alkylene wax), paraffin wax, etc. are listed.
  • the average particle size of the wax is preferably 50 nm or more and 5 ⁇ m or less, more preferably 100 nm or more and 1 ⁇ m or less, in order to prevent clogging of the inkjet head.
  • wax emulsions include, for example, AQUACER 515 (acid value: 5 mg KOH/g) manufactured by BYK Japan Co., Ltd., and HYTEC E-6500 (acid value: 10 to 20 mg KOH/g) manufactured by Toho Chemical Industry Co., Ltd.
  • the solid content of the resin emulsion in the ink composition is preferably 0.2% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less.
  • the ink composition according to this embodiment may contain an organic solvent in order to adjust the penetrability into a recording medium, the viscosity, drying property, defoaming property, etc. of the ink composition.
  • organic solvent include carboxylic acid amides such as N,N-dimethylformamide and N,N-dimethylacetamide; lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-methylpyrrolidin-2-one; cyclic ureas such as 1,3-dimethylimidazolidin-2-one and 1,3-dimethylhexahydropyrimid-2-one; ketones, ketoalcohols, and carbonates such as acetone, 2-methyl-2-hydroxypentan-4-one, and ethylene carbonate; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propyl, etc. of
  • oligo- or polyalkylene glycols or thioglycols having a C2-C6 alkylene unit such as butyl diol, 1,2-butylene glycol, 1,4-butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, and dithiodiglycol; C3-C9 polyols (triols), such as glycerin, diglycerin, hexane-1,2,6-triol, and trimethylolpropane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoallyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol monobutyl ether, di
  • the content of the organic solvent in the ink composition is preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.2% by mass or more and 35% by mass or less, even more preferably 1% by mass or more and 30% by mass or less, and particularly preferably 2% by mass or more and 20% by mass or less.
  • the ink composition according to the present embodiment may contain a viscosity modifier.
  • the viscosity range of the ink composition that can be ejected is usually determined based on the specifications of the inkjet head mounted thereon. For this reason, it is preferable to add a viscosity modifier to the ink composition to adjust the viscosity to an appropriate range.
  • the viscosity modifier is not particularly limited as long as it is a substance that can adjust the viscosity of the ink composition, except for the above-mentioned polymer dispersant, and known substances can be used. Specific examples thereof include organic solvents, hydrophilic resins, resin emulsions, and the like.
  • the ink composition according to this embodiment may contain a surfactant.
  • the surfactant include anionic, cationic, nonionic, silicone, and fluorine-based surfactants. Among these, cationic surfactants and nonionic surfactants are preferred.
  • anionic surfactants include alkyl sulfocarboxylates, ⁇ -olefin sulfonates, polyoxyethylene alkyl ether acetates, polyoxyethylene alkyl ether sulfates, N-acylamino acids or salts thereof, N-acylmethyltaurines, alkyl sulfates polyoxyalkyl ether sulfates, alkyl sulfates polyoxyethylene alkyl ether phosphates, rosin acid soaps, castor oil sulfates, lauryl alcohol sulfates, alkylphenol phosphates, alkyl phosphates, alkylaryl sulfonates, diethyl sulfosuccinates, diethylhexyl sulfosuccinates, dioctyl sulfosuccinates, etc.
  • cationic surfactants examples include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
  • Nonionic surfactants include, for example, ether-based surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl ethers having 4 to 18 carbon atoms (for example, polyoxyethylene butyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene 2-ethylhexyl ether, etc.), polyoxyethylene (di)styrenated phenyl ether (for example, Emulgen A-60, A-90, A-500 manufactured by Kao Corporation; DSP-9, DSP-12.5, TSP-7.5, KTSP-16, TSP-50 manufactured by Aoki Oil Industries Co., Ltd.); Examples of such esters include ethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbit
  • silicone surfactants include polyether-modified siloxane, polyether-modified polydimethylsiloxane, etc.
  • Specific examples of commercially available products include Dynol 960 and 980 manufactured by Air Products Co., Ltd.; Silface SAG001, SAG002, SAG003, SAG005, SAG503A, SAG008, SAG009, and SAG010 manufactured by Nissin Chemical Industry Co., Ltd.; BYK-345, 347, 348, 349, 3450, 3451, and 3455 manufactured by BYK Additives & Instruments Co., Ltd.; and TEGO Twin 4000, TEGO Wet KL 245, 250, 260, 265, 270, and 280 manufactured by Evonik Tego Chemie Co., Ltd.
  • fluorine-based surfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups on the side chains.
  • fluorine-based surfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups on the side chains.
  • Specific examples of commercially available products include Capstone FS-30 and FS-31 manufactured by Chemours.
  • preservatives examples include compounds such as organic sulfur compounds, organic nitrogen sulfur compounds, organic halogen compounds, haloarylsulfone compounds, iodopropargyl compounds, haloalkylthio compounds, nitrile compounds, pyridine compounds, 8-oxyquinolines, benzothiazole compounds, isothiazolinone compounds, dithiols, pyridine oxide compounds, nitropropane compounds, organic tin compounds, phenol compounds, quaternary ammonium salt compounds, triazine compounds, thiazine compounds, anilides, adamantane compounds, dithiocarbamates, brominated indanone compounds, benzyl bromoacetate compounds, inorganic salt compounds, etc.
  • Specific examples of commercially available products include Proxel GXL(S) and XL-2(S) manufactured by Arch Chemical Co., Ltd.
  • antifungal agents examples include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one, and salts thereof.
  • pH adjuster examples include alkanolamines such as diethanolamine, triethanolamine, and N-methyldiethanolamine; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonium hydroxide (aqueous ammonia); alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; alkali metal salts of organic acids such as potassium acetate; and inorganic bases such as sodium silicate and disodium phosphate.
  • alkanolamines such as diethanolamine, triethanolamine, and N-methyldiethanolamine
  • alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide
  • ammonium hydroxide aqueous ammonia
  • alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate
  • alkali metal salts of organic acids such as potassium acetate
  • inorganic bases such as sodium silicate and disodium phosphate.
  • chelating agent examples include disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracildiacetate, ⁇ -cyclodextrin, ⁇ -cyclodextrin, and ⁇ -cyclodextrin.
  • rust inhibitor examples include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.
  • Water-soluble UV absorber examples include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.
  • antioxidants for example, various organic and metal complex-based discoloration inhibitors can be used.
  • organic discoloration inhibitors include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, ascorbic acid, isoascorbic acid, chlorogenic acid, sulfur dioxide, catechins, dibutylhydroxytoluene, tocopherol, butylhydroxyanisole, and other compounds.
  • Examples of the defoaming agent include acetylene-based defoaming agents such as Surfynol 104 series (104A, 104E, 104H, 104PA, 104PG-50), Surfynol DF110D, Surfynol AD01, and Surfynol MD-20 (all manufactured by Nissin Chemical Industry Co., Ltd.); DF-58 (manufactured by Nissin Chemical Industry Co., Ltd.), BYK-017, BYK-018, BYK-019, BYK-021, BYK-022, BYK-023, BYK-024, BYK-025, BYK-028, BYK-044, BYK-092, BYK-1610, BYK-1611 , BYK-1615, BYK-1617, BYK-1650, BYK1679, BYK-1719, BYK-1723, BYK-1724, BYK-1730, BYK
  • the method for preparing the ink composition according to this embodiment is not particularly limited, and may employ known preparation methods using a ball mill, a sand mill, an attritor, a basket mill, a roll mill, etc.
  • Examples of the preparation method include a method of preparing an aqueous dispersion containing titanium oxide and a polymer dispersant, and adding water, a polyvalent metal salt, and, if necessary, an ink preparation agent to the aqueous dispersion and mixing them; a method of preparing an aqueous dispersion containing titanium oxide, a polymer dispersant, and a cationic resin, and adding water and, if necessary, an ink preparation agent to the aqueous dispersion and mixing them; and the like.
  • the ink composition according to this embodiment is preferably subjected to precision filtration using a membrane filter, glass filter paper, or the like.
  • a membrane filter, glass filter paper, or the like can be used.
  • the pore size of the filter, etc., used when performing precision filtration is usually 0.5 ⁇ m or more and 20 ⁇ m or less, preferably 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the pH of the ink composition according to this embodiment at 25°C is usually 5 or more and 11 or less, preferably 6 or more and 9 or less.
  • the surface tension of the ink composition according to this embodiment at 25°C is usually 20 mN/m or more and 60 mN/m or less, preferably 25 mN/m or more and 50 mN/m or less.
  • the viscosity of the ink composition according to this embodiment at 25°C is usually 2 mPa ⁇ s or more and 30 mPa ⁇ s or less, preferably 3 mPa ⁇ s or more and 15 mPa ⁇ s or less.
  • the pH, surface tension, and viscosity of the ink composition can be appropriately adjusted with a pH adjuster, a surfactant, an organic solvent, etc.
  • the ink composition according to this embodiment has excellent dispersion stability of titanium oxide and inkjet ejection properties, and also has excellent storage stability, redispersibility, and circulation stability of the ink composition.
  • the ink composition according to this embodiment has little coating unevenness during image formation and has excellent image forming properties.
  • the image recorded using the ink composition according to this embodiment has a large dot diameter, a good dot shape (e.g., the coffee stain phenomenon is suppressed), little graininess, good hue and color development, and excellent fastness properties such as abrasion resistance, heat abrasion resistance, light resistance, heat resistance, and oxidation gas resistance (e.g., ozone gas resistance).
  • the image recorded using an ink set including the ink composition according to this embodiment has little inter-color bleeding, little graininess in the printed parts of secondary or higher colors, and excellent solid uniformity in the printed parts of secondary or higher colors.
  • the ink composition according to this embodiment can be used in various printing processes.
  • it is suitable for writing instruments, various printing processes, information printing, textile printing, etc., and is particularly preferably used in inkjet printing.
  • a first aspect of the ink set according to this embodiment includes the ink composition according to this embodiment described above, and a white ink composition containing a white colorant and an anionic dispersant.
  • a second aspect of the ink set according to this embodiment includes the ink composition according to this embodiment described above, and a non-white ink composition containing a non-white colorant and an anionic dispersant.
  • the white ink composition contains a white colorant and an anionic dispersant. Each component contained in the white ink composition will be described in detail below. Each of the following components may be used alone or in combination of two or more.
  • the white ink composition contains a white coloring material.
  • the white coloring material may be titanium oxide or a white coloring material other than titanium oxide.
  • the white ink composition be such that the L * value of a coating obtained by coating the white ink composition is at least 68.
  • An example of a coating for measuring the L * value is a coating obtained by coating 50 ⁇ L of the white ink composition onto liner paper (K liner, manufactured by Daio Paper Corporation, weighing: 170 g/m 2 , brown liner with an L * value of 63) described below using a bar coater #8.
  • the content of the white colorant in the white ink composition is preferably 1% by mass or more and 30% by mass or less, more preferably 2% by mass or more and 25% by mass or less, even more preferably 5% by mass or more and 20% by mass or less, and particularly preferably 7% by mass or more and 18% by mass or less.
  • the white ink composition contains an anionic dispersant.
  • anionic dispersant include copolymers composed of at least two types of monomers (preferably at least one of which is a hydrophilic monomer) selected from monomers such as styrene and its derivatives; vinyl naphthalene and its derivatives; aliphatic alcohol esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids; (meth)acrylic acid and its derivatives; maleic acid and its derivatives; itaconic acid and its derivatives; fumaric acid and its derivatives; vinyl acetate, vinyl alcohol, vinyl pyrrolidone, acrylamide, and their derivatives.
  • copolymers examples include styrene-(meth)acrylic acid copolymers, styrene-(meth)acrylic acid-(meth)acrylic acid ester copolymers, (meth)acrylic acid ester-(meth)acrylic acid copolymers, polyethylene glycol (meth)acrylate-(meth)acrylic acid copolymers, and styrene-maleic acid copolymers.
  • Types of copolymers include block copolymers, random copolymers, and graft copolymers. These copolymers may be in the form of a salt.
  • the mass average molecular weight of the anionic dispersant is preferably 2,500 or more and 100,000 or less, and more preferably 7,000 or more and 25,000 or less.
  • the acid value of the anionic dispersant is preferably 50 mgKOH/g or more and 300 mgKOH/g or less, more preferably 80 mgKOH/g or more and 275 mgKOH/g or less, and even more preferably 80 mgKOH/g or more and 250 mgKOH/g or less.
  • Preferred anionic dispersants include the following two types of anionic dispersants:
  • the first anionic dispersant (Ac) is polyacrylic acid; polymethacrylic acid; or a copolymer of acrylic acid or methacrylic acid with at least two monomers selected from maleic acid and a sulfonic acid group-containing vinyl monomer.
  • a sulfonic acid group-containing vinyl monomer an unsaturated sulfonic acid monomer is preferable, and examples thereof include vinyl sulfonic acid, styrene sulfonic acid, and 2-acrylamido-2-methylpropane sulfonic acid.
  • These sulfonic acid group-containing vinyl monomers may form a salt. Examples of the salt include a sodium salt and a potassium salt.
  • the mass average molecular weight of the first anionic dispersant (Ac) is preferably 2,500 or more and 90,000 or less, and more preferably 4,000 or more and 60,000 or less.
  • the anionic group contained in the first anionic dispersant (Ac) may be neutralized with a base.
  • bases include organic amines such as ammonia, dimethylaminoethanol, and triethylamine; and alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide.
  • sodium hydroxide and potassium hydroxide are preferred from the viewpoint of dispersion stability.
  • the degree of neutralization of the first anionic dispersant (Ac) is preferably 30 mol% or more and 150 mol% or less. The degree of neutralization when neutralized with the theoretical equivalent of the acid value of the first anionic dispersant (Ac) is taken as 100%.
  • the first anionic dispersant (Ac) may be a commercially available product or may be synthesized.
  • Commercially available polymethacrylic acid includes, for example, polymethacrylic acid manufactured by Sigma-Aldrich.
  • Commercially available polyacrylic acid includes, for example, polyacrylic acid manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; Aron T-50 (mass average molecular weight: 6000), Aron A-10SL (mass average molecular weight: 5000), Aron A-30SL (mass average molecular weight: 6000) manufactured by Toa Gosei Co., Ltd.; Aqualic DL and Aqualic YS manufactured by Nippon Shokubai Co., Ltd.; and the like.
  • sulfonic acid group-containing polyacrylic acid includes, for example, Aron A-6012 (mass average molecular weight: 10000) manufactured by Toa Gosei Co., Ltd.; Aqualic GL and Aqualic LS manufactured by Nippon Shokubai Co., Ltd.
  • the white ink composition contains a first anionic dispersant (Ac)
  • its content is preferably 0.3% by mass or more and 20% by mass or less, more preferably 0.3% by mass or more and 10% by mass or less, even more preferably 0.3% by mass or more and 5% by mass or less, and particularly preferably 0.3% by mass or more and less than 1.0% by mass, relative to the content of the white colorant.
  • the second anionic dispersant (StAc) has, for example, 35% by mass or more and 85% by mass or less of constitutional units derived from at least one monomer selected from styrene and ⁇ -methylstyrene, and 8% by mass or more and 40% by mass or less of constitutional units derived from (meth)acrylic acid, and at least a part of the anionic groups is neutralized, and the degree of neutralization is 40 mol% or more and 150 mol% or less.
  • the proportion of constitutional units derived from at least one monomer selected from styrene and ⁇ -methylstyrene is preferably 38% by mass or more and 78% by mass or less, and more preferably 38% by mass or more and 75% by mass or less.
  • the proportion of constitutional units derived from (meth)acrylic acid is preferably 10% by mass or more and 35% by mass or less, and more preferably 10% by mass or more and 32% by mass or less.
  • the second anionic dispersant (StAc) may have structural units derived from other monomers.
  • examples of other monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth), t-butyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, ethyl ...
  • linear or branched alkyl (meth)acrylates such as uryl (meth)acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate; tetrahydrofuran (meth)acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, and isostearyl (meth)acrylate; (Meth)acrylates having a heterocyclic
  • the second anionic dispersant (StAc) may be a copolymer of polyalkylene glycol (meth)acrylate and (meth)acrylic acid.
  • polyalkylene glycol (meth)acrylate include methoxypolyethylene glycol mono(meth)acrylate, octoxypolyethylene glycol-polypropylene glycol mono(meth)acrylate, lauroxypolyethylene glycol mono(meth)acrylate, stearoxypolyethylene glycol mono(meth)acrylate, phenoxypolyethylene glycol mono(meth)acrylate, phenoxypolyethylene glycol-polypropylene glycol mono(meth)acrylate, nonylphenoxypolypropylene glycol mono(meth)acrylate, nonylphenoxypoly(ethylene glycol-propylene glycol) mono(meth)acrylate, etc.
  • the white ink composition contains a second anionic dispersant (StAc)
  • its content is preferably from 0.5% to 18% by mass, more preferably from 0.5% to 10% by mass, even more preferably from 0.5% to 5% by mass, and particularly preferably from 0.5% to 2.0% by mass, relative to the content of the white colorant.
  • the anionic dispersant can be prepared by copolymerizing a monomer mixture by a known polymerization method.
  • a solution polymerization method is preferred from the viewpoint of controlling the molecular weight.
  • Solvents used in the solution polymerization method include water; aliphatic alcohols having 1 to 3 carbon atoms, ketones having 3 to 8 carbon atoms, esters such as ethyl acetate, and mixed solvents of one or more of these with water; etc. Among these, water is preferred.
  • the amount of polymerization initiator used in the solution polymerization method is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, per 100 parts by mass of the total amount of monomers. Furthermore, the amount of polymerization initiator used is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, per 100 parts by mass of the total amount of monomers.
  • the amount of chain transfer agent used is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 0.8 parts by mass or more, per 100 parts by mass of the total amount of monomers. Furthermore, the amount of chain transfer agent used is preferably 8 parts by mass or less, more preferably 6 parts by mass or less, and even more preferably 4 parts by mass or less, per 100 parts by mass of the total amount of monomers.
  • Preferred polymerization conditions vary depending on the type of polymerization initiator, etc.
  • the polymerization temperature is preferably 50°C or higher and 90°C or lower, and the polymerization time is preferably 1 hour or higher and 20 hours or lower.
  • the polymerization temperature is preferably 70°C or higher, more preferably 75°C or higher, from the viewpoint of reactivity.
  • the polymerization temperature is preferably 85°C or lower, more preferably 83°C or lower, from the viewpoint of the molecular weight distribution of the resulting dispersant.
  • the polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas or argon gas.
  • the anionic dispersant can be isolated from the reaction solution by known methods such as reprecipitation and solvent distillation. After isolating the anionic dispersant, it is preferable to remove unreacted monomers, etc., by reprecipitation, membrane separation, chromatography, extraction, etc.
  • the anionic dispersant obtained has constituent units derived from anionic group-containing monomers, and can be ionized by neutralizing the anionic groups to make it water-soluble.
  • Neutralizing agents used for neutralization include ammonia; organic amines such as ethylamine, diethylamine, trimethylamine, triethylamine, and triethanolamine; and alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide.
  • alkali metal hydroxides are preferred, and sodium hydroxide is more preferred.
  • the white ink composition may contain water.
  • the water is preferably water with a low content of impurities such as metal ions, i.e., ion-exchanged water, distilled water, or the like.
  • the water content in the white ink composition is preferably 55% by mass or more and 90% by mass or less, and more preferably 60% by mass or more and 85% by mass or less.
  • the white ink composition may further contain an ink preparation agent in addition to the above-mentioned components.
  • the ink preparation agent include those exemplified in the ink composition according to the present embodiment described above. It is preferable that the white ink composition does not contain the above-mentioned aggregating agent.
  • the method for preparing the white ink composition is not particularly limited, and any known preparation method can be used.
  • the preparation method include a method in which an aqueous dispersion containing a white colorant and an anionic dispersant is prepared, and water and, if necessary, an ink preparation agent are added to the aqueous dispersion and mixed.
  • the white ink composition it is preferable to filter the white ink composition using a membrane filter, glass filter paper, or the like.
  • Non-white ink composition contains a non-white colorant and an anionic dispersant.
  • Each component contained in the non-white ink composition will be described in detail below.
  • Each of the following components may be used alone or in combination of two or more.
  • the non-white ink composition contains a non-white coloring material.
  • the non-white coloring material include pigments, disperse dyes, and solvent dyes. Among these, pigments are preferred from the viewpoint of image fastness such as light fastness and water fastness of the recorded image.
  • the pigment include inorganic pigments, organic pigments, and extender pigments.
  • inorganic pigments include carbon black, metal oxides, metal hydroxides, metal sulfides, metal ferrocyanides, and metal chlorides.
  • the inorganic pigment is preferably carbon black such as furnace black, lamp black, acetylene black, channel black, etc.
  • Commercially available carbon black products include, for example, Raven 760 ULTRA, Raven 780 ULTRA, Raven 790 ULTRA, Raven 1060 ULTRA, Raven 1080 ULTRA, Raven 1170, Raven 1190 ULTRA II, Raven 1200, Raven 1250, Raven 1255, Raven 1500, Raven 2000, Raven 2500U ULTRA, Raven 3500, Raven 5000 ULTRA II, Raven 5250, Raven 5750, Raven 7000 (all manufactured by Columbia Carbon); Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Regal 1330R, Regal 1400R, Regal 1500R, Regal 1600R, Regal 1700R, Regal 1800R, Regal 1900R, Regal 2000R, Regal 2100R, Regal 2200R, Regal 2300R, Regal 2400R, Regal 2500R, Regal 2600R
  • organic pigments include various pigments such as azo, disazo, phthalocyanine, quinacridone, isoindolinone, dioxazine, perylene, perinone, thioindigo, anthraquinone, and quinophthalone.
  • organic pigments include yellow pigments such as C.I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 24, 55, 73, 74, 75, 83, 93, 94, 95, 97, 98, 108, 114, 128, 129, 138, 139, 150, 151, 154, 155, 180, 185, 193, 199, 202, and 213; C.I.
  • extender pigments examples include silica, calcium carbonate, talc, clay, barium sulfate, and white carbon.
  • the non-white colorant preferably contains a pigment, and more preferably consists of a pigment.
  • the pigment it is preferable to use at least one selected from the group consisting of carbon black; C.I. Pigment Blue 15:3, 15:4; C.I. Pigment Yellow 74, 155; C.I. Pigment Red 122, 150; and C.I. Pigment Violet 19; and it is preferable to use at least one selected from the group consisting of carbon black; C.I. Pigment Blue 15:4; C.I. Pigment Yellow 155; C.I. Pigment Red 122, 150; and C.I. It is more preferable to use at least one selected from the group consisting of Pigment Violet 19.
  • disperse dyes include C.I. Disperse Yellow 3, 4, 5, 7, 9, 13, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68, 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 114, 116, 118, 119, 1 Yellow dyes such as C.I.
  • solvent dyes include yellow dyes such as C.I. Solvent Yellow 2, 6, 14, 16, 21, 25, 29, 30, 33, 51, 56, 77, 80, 82, 88, 89, 93, 116, 150, 160:1, 163, 179, etc.; orange dyes such as C.I. Solvent Orange 1, 2, 14, 45, 60, etc.; red dyes such as C.I. Solvent Red 1, 3, 7, 8, 9, 18, 19, 23, 24, 25, 27, 49, 100, 109, 121, 122, 125, 127, 130, 132, 135, 218, 225, 230, etc.; Violet dyes such as C.I. Solvent Violet 13 and 31; green dyes such as C.I. Solvent Green 3; brown dyes such as C.I.
  • Solvent Brown 3 and 5 blue dyes such as C.I. Solvent Blue 2, 11, 14, 24, 25, 35, 36, 38, 48, 55, 59, 63, 67, 68, 70, 73, 83, 105, 111, and 132; black dyes such as C.I. Solvent Black 3, 5, 7, 23, 27, 28, 29, and 34.
  • the L * value of a coated product of the non-white ink composition is less than 68.
  • An example of a coated product for measuring the L * value is a coated product obtained by applying 50 ⁇ L of the non-white ink composition to a liner paper (K liner, manufactured by Daio Paper Corporation, weighing: 170 g/m 2 , L * value: 63, brown liner) described below using a bar coater #8.
  • the content of the non-white colorant in the non-white ink composition is preferably 0.5% by mass or more and 30.0% by mass or less, more preferably 1.0% by mass or more and 10.0% by mass or less, even more preferably 2.0% by mass or more and 7.0% by mass or less, and particularly preferably 2.0% by mass or more and 6.0% by mass or less.
  • the non-white ink composition contains an anionic dispersant.
  • anionic dispersant include copolymers composed of at least two types of monomers (preferably at least one of which is a hydrophilic monomer) selected from monomers such as styrene and its derivatives, vinyl naphthalene and its derivatives, aliphatic alcohol esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, (meth)acrylic acid and its derivatives, maleic acid and its derivatives, itaconic acid and its derivatives, fumaric acid and its derivatives, vinyl acetate, vinyl alcohol, vinyl pyrrolidone, acrylamide, and their derivatives.
  • copolymers examples include styrene-(meth)acrylic acid copolymers, styrene-(meth)acrylic acid-(meth)acrylic acid ester copolymers, (meth)acrylic acid ester-(meth)acrylic acid copolymers, polyethylene glycol (meth)acrylate-(meth)acrylic acid copolymers, and styrene-maleic acid copolymers.
  • styrene-(meth)acrylic acid copolymer examples include block copolymers, random copolymers, and graft copolymers. These copoly
  • Anionic dispersants can be obtained commercially or synthesized.
  • anionic dispersants include, for example, Joncyrl 62 (mass average molecular weight: 13,000, acid value: 213 mg KOH/g), 67 (mass average molecular weight: 12,500, acid value: 213 mg KOH/g), 68 (mass average molecular weight: 13,000, acid value: 200 mg KOH/g), 586 (mass average molecular weight: 4,600, acid value: 108 mg KOH/g), 611 (mass average molecular weight: 8,100, acid value: 53 mg KOH/g), and 678 (mass average molecular weight: 8,600, acid value: 2 15mgKOH/g), 679 (mass average molecular weight: 9000, acid value: 200mgKOH/g), 680 (mass average molecular weight: 4500, acid value: 215mgKOH/g), 682 (mass average molecular weight: 1700, acid value: 238mgKOH/g), 683 (mass average molecular weight:
  • NS-2092 (mass average molecular weight: 9000, acid value: 200mgKOH/g), RS-1191 (mass average molecular weight: 6500, acid value: 280mgKOH/g), VS-1047 (mass average molecular weight: 10000, acid value: 240mgKO H/g), BS-1291 (mass average molecular weight: 10,000, acid value: 210 mgKOH/g), ZS-1417 (mass average molecular weight: 14,000, acid value: 156 mgKOH/g), US-1071 (mass average molecular weight: 1 Examples of styrene-acrylic copolymers include styrene-acrylic copolymers such as ...
  • a preferred example of an anionic dispersant obtained by synthesis is the A-B block copolymer disclosed in WO 2013/115071.
  • the mass average molecular weight of the anionic dispersant is preferably less than 50,000, more preferably from 3,000 to less than 50,000, and even more preferably from 7,000 to less than 25,000, from the viewpoints of storage stability of the dispersion liquid of the non-white colorant, improvement of ejection properties, and durability of the recorded image.
  • the acid value of the anionic dispersant is preferably from 50 mgKOH/g to 300 mgKOH/g, more preferably from 60 mgKOH/g to 275 mgKOH/g, and even more preferably from 70 mgKOH/g to 250 mgKOH/g.
  • the anionic dispersant can be used in a state where it is mixed with a non-white colorant. It can also be used in a state where the surface of the non-white colorant is partially or entirely covered with the dispersant. Alternatively, both of these states can be used in combination.
  • Anionic dispersants have salt-forming groups.
  • Salt-forming groups include carboxy, hydroxy, sulfo, phosphate, and amino groups.
  • Salt-forming groups can be introduced into anionic dispersants by polymerizing a monomer mixture that contains a salt-forming group-containing monomer.
  • the non-white ink composition is preferably prepared by preparing a dispersion containing a non-white colorant and an anionic dispersant, and then mixing it with other components.
  • a method for preparing a dispersion is the phase inversion emulsification method.
  • an anionic dispersant is dissolved in an organic solvent such as methyl ethyl ketone, and an aqueous solution of a neutralizing agent is added to prepare an emulsion.
  • a non-white colorant is added to the obtained emulsion, and a dispersion process is performed.
  • the organic solvent and some of the water are distilled off under reduced pressure from the liquid obtained in this manner, to obtain the desired dispersion.
  • the non-white ink composition may contain water.
  • the water is preferably water with a low content of impurities such as metal ions, i.e., ion-exchanged water, distilled water, or the like.
  • the water content in the non-white ink composition is preferably 55% by mass or more and 90% by mass or less, and more preferably 60% by mass or more and 85% by mass or less.
  • the non-white ink composition may further contain titanium oxide, ink preparation agents, etc.
  • titanium oxide and ink preparation agents include those exemplified in the ink composition according to the present embodiment described above. It is preferable that the non-white ink composition does not contain the above-mentioned aggregating agent.
  • the method for preparing the non-white ink composition is not particularly limited, and any known preparation method can be used.
  • the preparation method include a method in which an aqueous dispersion containing a non-white colorant and an anionic dispersant is prepared, and water and, if necessary, an ink preparation agent are added to the aqueous dispersion and mixed.
  • the non-white ink composition it is preferable to precisely filter the non-white ink composition using a membrane filter, glass filter paper, or the like.
  • the inkjet recording method according to this embodiment includes ejecting the ink composition according to this embodiment or each ink composition included in the ink set according to this embodiment from an inkjet head and depositing it onto a recording medium.
  • the recording medium according to this embodiment has the ink composition according to this embodiment or each ink composition included in the ink set according to this embodiment deposited thereon, and can be obtained by the inkjet recording method according to this embodiment.
  • inkjet printing methods include, for example, a charge control method, a drop-on-demand (pressure pulse) method, an acoustic inkjet method, and a thermal inkjet method, with the drop-on-demand method being preferred.
  • Inkjet printing methods also include a method of improving image quality by ejecting a large number of ink compositions with a small content of coloring material in a small volume; a method of improving image quality by using multiple ink compositions with substantially the same hue but different concentrations of coloring material in the ink composition; a method of improving the fixation of coloring material by using a colorless and transparent ink composition; and the like.
  • the inkjet head either one having an ink circulation mechanism or one not having an ink circulation mechanism can be used. From the viewpoint of suppressing the precipitation of titanium oxide, it is preferable to use an inkjet head having a circulation mechanism inside the head, that is, an inkjet head having a circulation mechanism.
  • An inkjet head having a circulation mechanism is, for example, an inkjet head having a plurality of droplet ejection elements, a common flow path communicating with each of the plurality of droplet ejection elements via a supply path, and a common circulation path communicating with each of the plurality of droplet ejection elements via a return path, and is equipped with an ink circulation device in which an ink composition is supplied from the common flow path to the plurality of droplet ejection elements and circulates through the common circulation path.
  • the circulation flow rate of the ink composition is not particularly limited, but is preferably 10 mL/min or more and 1000 mL/min or less, and more preferably 20 mL/min or more and 500 mL/min or less.
  • a line head type in which inkjet heads are arranged side by side is known.
  • the above-mentioned preferable circulation flow rate refers to the circulation flow rate for each inkjet head.
  • examples of inkjet heads equipped with a circulation mechanism include the SambaGL3 made by Fujifilm Corporation, the S series made by Canon Inc., and the KJ4B-EX1200 print head made by Kyocera Corporation.
  • each ink composition included in the ink set according to the present embodiment described above is applied to a recording medium, the ejection order of each ink composition is appropriately set according to the composition of the ink set.
  • the ink set includes the ink composition according to the present embodiment described above and a white ink composition containing a white colorant and an anionic dispersant
  • the order in which the two are ejected is not particularly limited. By applying both ink compositions so that they overlap in the same area of the recording medium, a printed matter with excellent white color development can be obtained. From the viewpoint of further increasing the whiteness, it is preferable that the ink composition according to the present embodiment is ejected before the white ink composition containing a white colorant and an anionic dispersant.
  • the ink set includes the ink composition according to the present embodiment described above and a non-white ink composition containing a non-white colorant and an anionic dispersant
  • the ink composition according to the present embodiment is ejected before the non-white ink composition containing a non-white colorant and an anionic dispersant.
  • the recording medium is not particularly limited as long as it is a material to which the ink composition can adhere, and examples of the recording medium include paper, film, cans, leather, cloth, and fiber.
  • Recording media are broadly divided into non-permeable recording media such as films and cans into which the ink composition does not permeate, and permeable recording media into which the ink composition permeates, with permeable recording media being preferred.
  • permeable recording media include plain paper, inkjet paper, art paper, coated paper, matte paper, cast paper, and liner paper.
  • liner paper is preferred as a recording medium.
  • Liner paper is cardboard liner paper described in Japanese Industrial Standard JIS P3902:2011 "Corrugated cardboard liners” and is made primarily from recycled paper and kraft pulp.
  • the liner paper after it has been processed into cardboard is also the subject of recording.
  • the liner paper on the surface after it has been processed and formed into a cardboard box is also the subject of recording.
  • the liner paper may be non-white liner paper.
  • liner paper is often made from recycled paper and is often not white.
  • Such non-white liner paper tends to have poor color development in the recorded image formed on its surface, but the inkjet recording method according to this embodiment makes it possible to form a recorded image with excellent color development.
  • the surface of the liner paper may be provided with a coating layer or may be subjected to a surface treatment.
  • surface treatments include water-repellent treatment, anti-fouling treatment, and coloring treatment.
  • water-repellent treatment when a water-based ink composition is applied to the surface, the ink composition is repelled, and unevenness in the image is likely to occur.
  • the water-repellent treatment can be performed by applying a water-repellent agent, and there are commercially available products such as cardboard that contain water-repellent liner paper.
  • the acid value (mgKOH/g) was measured in accordance with the potentiometric method of JIS K0070, and the obtained value was converted into 100% nonvolatile content.
  • amine value (mgKOH/g) was measured according to the potentiometric titration method of JIS K7237, and the obtained value was converted into 100% nonvolatile content.
  • the particle size was measured using a dynamic light scattering particle size distribution analyzer nanotrac WAVE II manufactured by Microtrac Bell Co., Ltd.
  • the titanium oxide concentration was adjusted with water to 0.075%, and the measurement was performed.
  • the median diameter (D50, number average particle diameter) value at this time was taken as the average particle diameter of the particles in the dispersion.
  • Preparation of titanium oxide dispersions Dp1-1 to Dp1-6> The components shown in Table 1 below were charged and dispersed in a sand grinder using zirconia beads with a particle size of 0.3 mm at 1500 rpm for 3 hours. The resulting dispersion was filtered through a glass fiber filter (GC-50, manufactured by Advantec Corporation) to obtain titanium oxide dispersions Dp1-1 to Dp1-6.
  • Examples 1 to 15 Preparation of Inks A1-1 to A1-15>
  • the components shown in Tables 2 and 3 were thoroughly mixed and filtered through a mixed cellulose ester filter having a pore size of 5 ⁇ m, and then degassed using a vacuum pump to obtain inks A1-1 to A1-15.
  • the numerical value in the column for each component in Tables 2 and 3 indicates the amount (parts) of the component added, and a blank space means that the component was not used.
  • Each of the inks prepared in Examples 1 to 15 was ejected onto HEIKO cut paper color wood-free black (manufactured by Shimojima Co., Ltd.) using a printer equipped with an inkjet head KJ4B-YH (600 dpi x 600 dpi) manufactured by Kyocera Corporation at a droplet size of 12 pL and a speed of 25 m/min to perform inkjet recording, thereby obtaining an initial printed image.
  • Inkjet recording was performed so as to obtain a solid image with a duty of 100%.
  • Evaluations A, B, and C indicate good inkjet dischargeability, and evaluation D indicates poor inkjet dischargeability.
  • D The area of the printed image after 3 minutes is less than 60% compared to the initial printed image.
  • magenta dispersion 27.78 parts
  • 1,4-butanediol 5.00 parts
  • propylene glycol 25.00 parts
  • Surfynol 485 manufactured by Nissin Chemical Industry Co., Ltd.
  • water 42.12 parts
  • the magenta OD value of the areas that were coated so as to overlap with the inks of Examples 1 to 15 was compared with the magenta OD value of the areas that were coated so as not to overlap with the inks of Examples 1 to 15, and the color development was evaluated according to the following evaluation criteria. Evaluations A, B, and C indicate good color development, and evaluation D indicates poor color development. -Evaluation criteria- A: The rate of change in magenta OD value is greater than 25%. B: The rate of change in magenta OD value is 10% or more and 25% or less. C: The rate of change in magenta OD value is 5% or more and less than 10%. D: The rate of change in magenta OD value is less than 5%.
  • inks A1-1 to A1-15 of Examples 1 to 15 had good dispersion stability, inkjet ejection properties, and color development properties.
  • ⁇ Preparation Example 7 Preparation of anionic dispersant aqueous solution Ac-2> DL-453 (polyacrylic acid, manufactured by Nippon Shokubai Co., Ltd., mass average molecular weight: 50,000, non-volatile content: 35%) was used as an anionic dispersant aqueous solution Ac-2 without pH adjustment.
  • the pH of the anionic dispersant aqueous solution Ac-2 was 8.4.
  • the dynamic surface tension of an aqueous solution with a non-volatile content of 10% was measured by the maximum bubble pressure method at a life of 0.1 sec, it was 72 mN/m.
  • ⁇ Preparation Example 8 Preparation of anionic dispersant aqueous solution Ac-3> YS-100 (polyacrylic acid, manufactured by Nippon Shokubai Co., Ltd., mass average molecular weight: 5000, non-volatile content: 45%) was used as it is as anionic dispersant aqueous solution Ac-3 without pH adjustment.
  • the pH of the anionic dispersant aqueous solution Ac-3 was 8.4.
  • the dynamic surface tension of an aqueous solution with a non-volatile content of 10% was measured by the maximum bubble pressure method with a life of 0.1 sec, it was 73 mN/m.
  • the obtained anionic dispersants StAc-4 to StAc-5, neutralizer, and water were charged in the amounts (units: parts) shown in Table 6 below, heated to 80°C, and stirred for 2 hours to obtain aqueous anionic dispersant solutions StAc-4 to StAc-5 (non-volatile content: 20%).
  • Preparation of titanium oxide dispersions Dp3-1 to Dp3-6> The components shown in Table 7 below were charged and dispersed in a sand grinder using zirconia beads with a particle size of 0.3 mm at 1500 rpm for 3 hours. The resulting dispersion was filtered through a glass fiber filter (GC-50, manufactured by Advantec Corporation) to obtain titanium oxide dispersions Dp3-1 to Dp3-6.
  • Preparation of Inks B1 to B6> The components shown in Table 8 below were thoroughly mixed and filtered through a mixed cellulose ester filter with a pore size of 5 ⁇ m, and then degassed using a vacuum pump to obtain inks B1 to B6.
  • the numerical value in the column for each component in Table 8 indicates the amount (parts) of the component added.
  • a liner paper (K liner, Daio Paper Co., Ltd., brown liner with basis weight: 170 g/ m2 , L * value: 63) was coated with 50 ⁇ L of the first color ink shown in Table 9 below using bar coater #8, and then dried for 15 minutes in a thermostatic bath at 120° C. The removed print was coated with the second color ink shown in Table 9 below under the same conditions, so as to create areas that overlapped with the first color ink and areas that did not, to prepare a test piece.
  • the abrasion resistance of each test piece was evaluated using a No. 428 Gakushin abrasion tester (friction tester type II) manufactured by Yasuda Seiki Seisakusho Co., Ltd.
  • the image portion was rubbed 40 times with a load of 500 g applied to the test piece, and the degree of deterioration of the recorded image was evaluated for abrasion resistance according to the following evaluation criteria.
  • B Slight scratches were observed on the recorded image.
  • D The scratches on the recorded image were very large.
  • Preparation of titanium oxide dispersions Dp2-1 to Dp2-13> The components shown in Tables 11 and 12 below were charged and dispersed in a sand grinder using zirconia beads with a particle size of 0.3 mm at 1500 rpm for 3 hours. The resulting dispersion was filtered through a glass fiber filter (GC-50, manufactured by Advantec Corporation) to obtain titanium oxide dispersions Dp2-1 to Dp2-13.
  • GC-50 glass fiber filter
  • Examples 32 to 46 Preparation of Inks A2-1 to A2-15>
  • the components shown in Tables 13 and 14 were thoroughly mixed and filtered through a mixed cellulose ester filter having a pore size of 5 ⁇ m, and then degassed using a vacuum pump to obtain inks A2-1 to A2-15.
  • the numerical values in the columns for each component in Tables 13 and 14 indicate the amount (parts) of the component added.
  • the initial particle size (D50) of titanium oxide was measured, and the dispersibility was evaluated according to the following evaluation criteria: Ratings A, B, and C indicate good dispersibility, and rating D indicates poor dispersibility.
  • Ratings A, B, and C indicate good dispersibility, and rating D indicates poor dispersibility.
  • C D50 is more than 400 nm and less than 450 nm.
  • D D50 is greater than 450 nm.
  • inks A2-1 to A2-15 of Examples 32 to 46 had good dispersibility, dispersion stability, inkjet dischargeability, whiteness, and color development.
  • a liner paper (K liner, Daio Paper Co., Ltd., brown liner with basis weight: 170 g/ m2 , L * value: 63) was coated with 50 ⁇ L of the first color ink shown in Table 16 below using bar coater #8, and then dried for 15 minutes in a thermostatic bath at 120° C. The removed print was coated with the second color ink shown in Table 16 below under the same conditions, so as to create areas that overlapped with the first color ink and areas that did not, to prepare a test piece.

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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)

Abstract

L'invention concerne une composition d'encre qui contient un oxyde de titane, un dispersant polymère et un floculant, et dans laquelle la teneur en oxyde de titane est d'au moins 1 % en masse et inférieure à 30 % en masse. L'invention concerne également un ensemble d'encres comprenant la composition d'encre, un support d'impression auquel adhère la composition d'encre, et un procédé d'impression à jet d'encre utilisant la composition d'encre.
PCT/JP2024/002750 2023-01-31 2024-01-30 Composition d'encre, ensemble d'encres, support d'impression et procédé d'impression à jet d'encre Ceased WO2024162297A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140118449A1 (en) * 2011-06-10 2014-05-01 Hewlett-Packard Development Company, L.P. White pre-treatment composition
JP2018058919A (ja) * 2016-09-30 2018-04-12 株式会社パイロットコーポレーション 筆記具用水性インキ組成物、およびそれを用いた筆記具
JP2019070107A (ja) * 2017-10-06 2019-05-09 株式会社リコー インクセット、白色インク、記録方法、インク吐出装置
JP2019155903A (ja) * 2018-03-06 2019-09-19 株式会社リコー 液体組成物、液体組成物付与装置、画像形成装置、及び画像形成方法
JP2020111708A (ja) * 2019-01-16 2020-07-27 サカタインクス株式会社 アンカーコート剤
JP2022089272A (ja) * 2020-12-04 2022-06-16 東洋インキＳｃホールディングス株式会社 有彩色プロセスカラーインクジェットインキ
JP2023148523A (ja) * 2022-03-30 2023-10-13 キヤノン株式会社 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 (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140118449A1 (en) * 2011-06-10 2014-05-01 Hewlett-Packard Development Company, L.P. White pre-treatment composition
JP2018058919A (ja) * 2016-09-30 2018-04-12 株式会社パイロットコーポレーション 筆記具用水性インキ組成物、およびそれを用いた筆記具
JP2019070107A (ja) * 2017-10-06 2019-05-09 株式会社リコー インクセット、白色インク、記録方法、インク吐出装置
JP2019155903A (ja) * 2018-03-06 2019-09-19 株式会社リコー 液体組成物、液体組成物付与装置、画像形成装置、及び画像形成方法
JP2020111708A (ja) * 2019-01-16 2020-07-27 サカタインクス株式会社 アンカーコート剤
JP2022089272A (ja) * 2020-12-04 2022-06-16 東洋インキＳｃホールディングス株式会社 有彩色プロセスカラーインクジェットインキ
JP2023148523A (ja) * 2022-03-30 2023-10-13 キヤノン株式会社 インクジェット記録方法、及びインクジェット記録装置

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