WO2024084890A1 - インクセット及びインクジェット記録方法 - Google Patents

インクセット及びインクジェット記録方法 Download PDF

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Publication number
WO2024084890A1
WO2024084890A1 PCT/JP2023/034414 JP2023034414W WO2024084890A1 WO 2024084890 A1 WO2024084890 A1 WO 2024084890A1 JP 2023034414 W JP2023034414 W JP 2023034414W WO 2024084890 A1 WO2024084890 A1 WO 2024084890A1
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Prior art keywords
ink
treatment liquid
range
pigment
polyolefin resin
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PCT/JP2023/034414
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English (en)
French (fr)
Japanese (ja)
Inventor
直人 新妻
諒 田口
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Konica Minolta Inc
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Konica Minolta Inc
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Priority to CN202380071341.5A priority Critical patent/CN119998414A/zh
Priority to JP2024551363A priority patent/JPWO2024084890A1/ja
Priority to EP23879538.9A priority patent/EP4606872A4/en
Publication of WO2024084890A1 publication Critical patent/WO2024084890A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/108—Hydrocarbon resins
    • 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
    • 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
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • 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
    • B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
    • B41M5/0017—Application of ink-fixing material, e.g. mordant, precipitating agent, on the substrate prior to printing, e.g. by ink-jet printing, coating or spraying

Definitions

  • the present invention relates to an ink set and an inkjet recording method.
  • the present invention aims to provide an ink set and the like that has good ink storage stability, high image quality, and good adhesion to non-absorbent substrates in a two-liquid inkjet recording method.
  • Inkjet recording on packaging materials requires substrate versatility that can be used with these multiple substrate types, which has been an issue.
  • a surface that has poor ink wettability such as a polypropylene surface that has not been corona discharge-treated or a gravure ink surface
  • the ink droplets tend to coalesce together, which is known to make it difficult to form an image.
  • a method is taken in which the wettability of the ink is increased by adding a surfactant or a wetting solvent.
  • polyolefin resins are designed to have a small number of hydrophilic groups on the resin surface from the viewpoint of adhesion to plastic substrates, and the amount of dispersion aid added is also kept to a minimum. For this reason, adding large amounts of surfactants or wetting solvents that increase wettability to inks containing polyolefin resins is not desirable from the viewpoint of ink stability.
  • the present invention was made in consideration of the above problems and circumstances, and the problem to be solved is as follows: To provide an ink set and inkjet recording method in a two-liquid inkjet recording system, which has good ink storage stability, high image quality, and good adhesion to non-absorbent substrates.
  • the present inventors have discovered the importance of setting the static and dynamic surface tensions of the treatment liquid within a specific range in the process of investigating the causes of the above problems. This makes it possible to provide an ink set and an inkjet recording method that have excellent image quality and good adhesion to non-absorbent substrates, even for inks containing polyolefin resins. That is, the above-mentioned problems of the present invention are solved by the following means.
  • An ink set for forming an image by applying and uniting the ink and the treatment liquid onto a recording medium including at least a pigment and a treatment liquid including at least a flocculant,
  • the static surface tension of the treatment liquid is within a range of 18 to 25 mN/m at 25° C.
  • the dynamic surface tension of the treatment liquid during a surface life of 50 msec is within a range of 25 to 35 mN/min at 25° C.
  • the ink contains a polyolefin resin, and The ink set, wherein the recording medium is a non-absorbent substrate.
  • the static surface tension of the ink is within the range of 25 to 35 mN/m at 25° C.; 2.
  • An inkjet recording method comprising recording an image on a recording medium by using the ink set according to any one of items 1 to 8.
  • the present invention it is possible to provide an ink set and an ink jet recording method which have good ink storage stability, excellent image quality, and excellent adhesion to non-absorbent substrates in a two-liquid ink jet recording system.
  • the mechanism by which the effects of the present invention are manifested or the mechanism by which the effects of the present invention are acted upon has not been clearly understood, it is speculated as follows.
  • the static surface tension and dynamic surface tension of the treatment liquid are set to be within the specific range. If the static surface tension and dynamic surface tension are lower than the specific range, the treatment liquid spreads and wets too much, resulting in poor character reproducibility.
  • the static surface tension and dynamic surface tension are higher than the specific range, the treatment liquid is repelled by the substrate, resulting in poor character reproducibility.
  • the static surface tension and dynamic surface tension of the treatment liquid are higher than the specific range, the treatment liquid is repelled by the substrate, resulting in poor character reproducibility.
  • the static surface tension and dynamic surface tension of the treatment liquid are within a specific range, it is possible to minimize the addition of surfactants and wetting solvents that increase wettability to the ink.
  • a surfactant even if a surfactant is used, it is possible to use one that does not adversely affect the storage stability of the ink, or to limit its use to a level that does not adversely affect the storage stability.
  • a polyolefin resin when a polyolefin resin is used, this effect is extremely effective.
  • the ink has excellent adhesion to a non-absorbent substrate.
  • the two particle size ranges are preferably an average particle size range of 10 to 80 nm and an average particle size range of 100 to 300 nm.
  • a small-diameter polyolefin resin may be mixed with a large-diameter resin other than polyolefin resin.
  • FIG. 1 is a diagram for explaining a state in which the treatment liquid and the ink are combined in the present invention
  • FIG. 1 is a diagram for explaining a state in which the treatment liquid and the ink are combined in the present invention
  • FIG. 1 is a diagram for explaining a state in which the treatment liquid and the ink are combined in the present invention
  • FIG. 1 is a schematic diagram showing an example of a recording device preferred for the present invention.
  • the ink set of the present invention comprises an ink containing at least a pigment and a treatment liquid containing at least a flocculant, and is an ink set for forming an image by applying the ink and the treatment liquid onto a recording medium and allowing them to coalesce, wherein the static surface tension of the treatment liquid is within a range of 18 to 25 mN/m at 25°C, and the dynamic surface tension of the treatment liquid at a surface life of 50 msec is within a range of 25 to 35 mN/min at 25°C, the ink contains a polyolefin resin, and the recording medium is a non-absorbent substrate.
  • This feature is a technical feature common to or corresponding to each of the following embodiments.
  • the static surface tension of the ink is preferably within the range of 25 to 35 mN/m at 25°C.
  • the dynamic surface tension of the ink during a surface life of 50 msec is preferably within the range of 35 to 45 mN/min at 25°C.
  • the polyolefin resin is an acid-modified polyolefin resin, since this allows high character reproducibility to be obtained in a two-liquid inkjet recording method.
  • the treatment liquid contains a trisiloxane-based surfactant, since this allows high character reproducibility to be obtained in a two-liquid inkjet recording method.
  • the ink contains polyolefin resin particles having an average particle size (average particle diameter) in the range of 10 to 80 nm and resin particles having an average particle size in the range of 100 to 300 nm.
  • the resin particles having an average particle size in the range of 100 to 300 nm may be resin particles other than polyolefin resin particles, but are preferably polyolefin resin particles.
  • the average particle size of the resin particles is set within the above range is that if the average particle size is 10 nm or more, the film-forming property of the resin during drying of the ink is not too high, and nozzle clogging can be prevented. Also, if the average particle size of the resin particles is 300 nm or less, the particle size is not too large, and therefore the ejection property by an inkjet head is good. As a result, the film-forming property and the adhesion to the substrate are also good.
  • the average particle size of the pigment particles contained in the pigment is within the range of 50 to 100 nm, as this provides excellent ink adhesion to non-absorbent substrates.
  • the ink contains wax, since this provides excellent ink adhesion to non-absorbent substrates.
  • the inkjet recording method of the present invention uses the ink set to record an image on a recording medium.
  • the ink has good storage stability, and is excellent in image quality and adhesion to non-absorbent substrates.
  • the amount of the treatment liquid applied per unit area on which the image is formed is 5.0 g/m 2 or less, in that high character reproducibility can be obtained in a two-liquid inkjet recording method.
  • the ink set of the present invention comprises an ink containing at least a pigment and a treatment liquid containing at least a flocculant, and is an ink set for forming an image by applying the ink and the treatment liquid onto a recording medium and allowing them to coalesce, wherein the static surface tension of the treatment liquid is within a range of 18 to 25 mN/m at 25°C, and the dynamic surface tension of the treatment liquid at a surface life of 50 msec is within a range of 25 to 35 mN/min at 25°C, the ink contains a polyolefin resin, and the recording medium is a non-absorbent substrate.
  • treatment liquid and "ink” referred to in this invention refer to a “treatment liquid (also called a “pretreatment liquid” or “primer”) and an “ink (also called a “water-based ink” or “aqueous ink”)” that use at least water or a water-soluble solvent as the solvent. In both cases, it is preferable that 60% by mass or more of the solvent used is “water”.
  • combining refers to causing droplets of the treatment liquid and the ink to overlap or come into contact with each other on the recording medium, so that the respective components mix together to form a single liquid body, ultimately forming a single pixel that constitutes an image.
  • droplets 12 of treatment liquid are caused to land on the recording medium F via an inkjet head.
  • droplets 22 of ink are caused to land on the recording medium F on which the treatment liquid has landed.
  • droplets 12 of treatment liquid and droplets 22 of ink are mixed, and the pigment P in the ink is aggregated and precipitated by the aggregating agent in the treatment liquid.
  • An image layer G is then formed on the recording medium F. It should be noted that the ink may be caused to land on the recording medium first, and then the treatment liquid may be caused to land on the recording medium.
  • the term “static surface tension” refers to the surface tension when the liquid surface approaches an equilibrium state as the components of the ink or treatment liquid diffuse over the course of the surface life.
  • the static surface tension of the ink or treatment liquid can be measured using a platinum plate with an automatic surface tensiometer (for example, model "CBVP-Z” manufactured by Kyowa Interface Science Co., Ltd.) Unless otherwise specified, the static surface tension in this specification is the static surface tension measured at 25°C.
  • the static surface tension of the treatment liquid is within the range of 18 to 25 mN/m at 25° C.
  • the reason why the static surface tension of the treatment liquid is set within the above range is that if it is lower than 18 mN/m, the treatment liquid will expand and spread too much, resulting in poor character reproducibility, whereas if the static surface tension of the treatment liquid is higher than 25 mN/m, the treatment liquid will be repelled by the substrate, resulting in poor character reproducibility.
  • the static surface tension of the ink is preferably within the range of 25 to 35 mN/m at 25° C.
  • the term “dynamic surface tension” refers to the surface tension immediately after the formation of a liquid surface (gas-liquid interface) when the liquid surface is in a non-equilibrium state, and is a value measured at 25°C by a maximum bubble pressure method.
  • the "surface life” is the time elapsed since the liquid surface was formed, that is, the life of the bubble generated in the maximum bubble pressure method, and is also called the bubble lifetime. Specifically, it refers to the time from when a new interface is generated within the tip of the probe of the dynamic surface tensiometer to when the maximum bubble pressure is reached.
  • the dynamic surface tension of the treatment liquid or ink can be measured using a dynamic surface tensiometer, such as a bubble pressure dynamic surface tensiometer (manufactured by KRUSS, model "BP100"). Unless otherwise specified, the dynamic surface tension in this specification is the dynamic surface tension measured at 25° C. for 15 ms using the maximum bubble pressure method.
  • the dynamic surface tension of the treatment liquid at a surface life of 50 msec is within the range of 25 to 35 mN/m at 25° C.
  • the reason why the dynamic surface tension of the treatment liquid is set within the above range is that if it is lower than 25 mN/m, the treatment liquid will expand and spread too much, resulting in poor character reproducibility, whereas if the dynamic surface tension of the treatment liquid is higher than 35 mN/m, the treatment liquid will be repelled by the substrate, resulting in poor character reproducibility.
  • the dynamic surface tension of the ink at a surface life of 50 msec is preferably within the range of 35 to 45 mN/min at 25° C.
  • the type and content of the surfactant In order to set the static surface tension and dynamic surface tension of the treatment liquid within the above ranges, respectively, it is possible to control the type and content of the surfactant, the type and content of the water-soluble solvent, and the type and content of the coagulant, etc. Specifically, it is preferable to use various polyether-modified silicones and/or acetylene glycol-based surfactants as the surfactant contained in the treatment liquid. In particular, it is preferable to use trisiloxane-based surfactants. It is also preferable to set the content of the surfactant within the range of 0.1 to 2.0 mass % of the treatment liquid.
  • a water-soluble solvent having an SP value of 24 (J/cm 3 ) 1/2 or more and a boiling point in the range of 150° C. to 250° C., and to set the content thereof in the range of 5 to 40 mass %.
  • the flocculant for example, an organic acid, a polyvalent metal salt, a soluble cationic polymer, or the like is used as described below, and the content of the flocculant in the treatment liquid is preferably within the range of 1 to 8% by mass. It is further preferable that the content is within the range of 1 to 4% by mass.
  • the type and content of the surfactant In order to set the static surface tension and dynamic surface tension of the ink within the above ranges, respectively, it is possible to control the type and content of the surfactant, the type and content of the water-soluble solvent, the type and content of the pigment dispersant, the type and content of the resin particles, the type and content of the additives, etc. Note that a surfactant that does not impair the storage stability of the ink is used, or a surfactant is used in an amount that does not impair the storage stability.
  • the surfactant contained in the ink it is preferable to use various polyether-modified silicones and/or acetylene glycol-based surfactants as the surfactant contained in the ink, and it is preferable to set the content of the surfactant within the range of 0.1 to 2.0% by mass relative to the ink.
  • the water-soluble solvent used has an SP value of 24 (J/cm 3 ) 1/2 or more and a boiling point in the range of 150° C. to 250° C., and the content thereof is preferably in the range of 5 to 40 mass %.
  • the pigment dispersant it is preferable to use various low molecular weight dispersants, nonionic polymer dispersants, anionic polymer dispersants, or resin-coated pigment dispersions as appropriate.
  • the type of resin fine particles it is preferable to use resin fine particles of polyolefin resin, and the content of the resin fine particles in the ink is within the range of 1 to 15% by mass.
  • the polyolefin resin preferably contains resin particles having an average particle size within a range of 10 to 80 nm and resin particles having an average particle size within a range of 100 to 300 nm. It is also preferable to use wax as an additive, and the content of wax in the ink is preferably within a range of 0.1 to 5% by mass.
  • the treatment liquid according to the present invention can accelerate the formation of an ink image by aggregating or thickening the ink when an image is recorded on a substrate by inkjet printing.
  • the treatment liquid according to the present invention contains at least a flocculant. It is also preferable that the treatment liquid contains a water-soluble solvent, a surfactant, and water.
  • the treatment liquid according to the present invention contains a material that generates aggregates when it comes into contact with ink, that is, an aggregating agent which is a polyvalent metal salt.
  • the aggregating agent enhances the interaction with the ink, and can more firmly fix the ink dots.
  • the polyvalent metal salt can aggregate anionic components (usually coloring materials, pigments, etc., which will be described later) in the ink by salting out.
  • the polyvalent metal salt may be a salt of a metal having a valence of 2 or more.
  • the type of metal (cation) constituting the polyvalent metal salt is not particularly limited, and examples thereof include divalent metal ions such as Ca2 + , Cu2 + , Ni2 + , Mg2 + , Zn2 + , and Ba2 + , trivalent metal ions such as Al3 + , Fe3 + , Cr3 + , and Y3 + , and tetravalent metal ions such as Zr4 + , etc.
  • the type of salt constituting the polyvalent metal salt is not particularly limited, but for example, known salts such as carbonates, sulfates, nitrates, hydrochlorides, organic carboxylates, organic sulfonates, borates, phosphates, hydrobromides, hydroiodides, and thiocyanates can be used.
  • the organic carboxylate include acetic acid, oxalic acid, lactic acid, fumaric acid, citric acid, salicylic acid, and benzoic acid.
  • polyvalent metal salts include calcium chloride, magnesium chloride, calcium nitrate, magnesium nitrate, magnesium acetate, calcium acetate, magnesium lactate, calcium pantothenate, and other calcium or magnesium salts of carboxylic acids.
  • the treatment liquid according to the present invention may further contain an organic acid as a flocculant in addition to the polyvalent metal salt.
  • the organic acid contained in the treatment liquid as an aggregating agent is capable of aggregating the coloring material contained in the ink, and preferably has a first dissociation constant of 3.5 or less.
  • the first dissociation constant is within the range of 1.5 to 3.5.
  • preferred organic acids to be contained in the flocculant include formic acid, acetic acid, propionic acid, isobutyric acid, oxalic acid, fumaric acid, malic acid, citric acid, malonic acid, succinic acid, maleic acid, benzoic acid, 2-pyrrolidone-5-carboxylic acid, lactic acid, acrylic acid and its derivatives, methacrylic acid and its derivatives, acrylamide and its derivatives, and other compounds having a carboxy group, sulfonic acid derivatives, or phosphoric acid and its derivatives.
  • organic acids that are not completely neutralized with a base.
  • Neutralization with a base means that the acidic groups of these acids are ionic-bonded with other positively charged elements or compounds (e.g., inorganic compounds such as metals).
  • not completely neutralized means that among the acidic groups of the organic acid, there are acidic groups that do not form the above-mentioned ionic bonds.
  • preferred organic acids include formic acid, acetic acid, propionic acid, benzoic acid, etc.
  • the treatment liquid according to the present invention may further contain an inorganic acid as an aggregating agent, which is capable of aggregating anionic components in the ink by varying the pH.
  • the inorganic acid is capable of agglomerating pigments that may be contained in the ink, which will be described later.
  • examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, and sulfamic acid.
  • a soluble cationic polymer may also be used as the flocculant.
  • the dissolved cationic polymer contained in the treatment liquid include polyallylamine, polyvinylamine, polyethyleneimine, and polydiallyldimethylammonium chloride.
  • examples of commercially available dissolving cationic polymers include KHE100L and FPA100L manufactured by Senka Corporation, and PAS-92A, PAS-M-1A, and PAS-21CL manufactured by Nittobo Medical Co., Ltd.
  • the content of the polyvalent metal salt is preferably in the range of 0.5 to 20% by mass, and more preferably in the range of 1 to 10% by mass, relative to 100% by mass of the total mass of the treatment liquid, which is preferable from the viewpoint of effectively aggregating anionic components in the ink and balancing image quality and hot water resistance.
  • the content of the organic acid is preferably within a range of 0.1 to 10 mass %, and more preferably within a range of 1 to 3 mass %, relative to 100 mass % of the total mass of the treatment liquid.
  • the content of the inorganic acid is preferably within the range of 0.1 to 10 mass %, and more preferably within the range of 1 to 3 mass %, relative to 100 mass % of the total mass of the treatment liquid.
  • the content of polyvalent metal salts or organic acids in the aqueous solution can be measured by known methods.
  • the content of polyvalent metal salts can be measured by ICP emission analysis, and the content of organic acids can be measured by high performance liquid chromatography (HPLC).
  • the amount of organic acid applied is preferably an amount that adjusts the pH of the treatment liquid to be equal to or less than the neutralization equivalent of the anionic component contained in the ink.
  • the anionic component is a compound having a carboxy group, it is preferable that the first dissociation constant of the organic acid is 3.5 or less, from the viewpoint of making the image less susceptible to bleeding.
  • the water-soluble solvent contained in the treatment liquid according to the present invention is preferably a water-soluble solvent having a boiling point within the range of 150 to 250°C.
  • water-soluble solvents include alcohols, polyhydric alcohols, amines, amides, glycol ethers, and 1,2-alkanediols having 4 or more carbon atoms. It is also preferable to use a water-soluble solvent having an SP value of 24 (J/cm 3 ) 1/2 or more.
  • the cloud point of the treatment liquid is lowered, which makes it possible to heat the treatment liquid to a temperature above its cloud point during the ink drying process, thereby obtaining images with particularly good adhesion to non-absorbent substrates.
  • the SP value is called the solubility parameter.
  • the SP value in the present invention is a value calculated by the Fedors method. It is obtained from the molar heat of vaporization of the water-soluble solvent and the molar volume of the water-soluble solvent at 25°C.
  • water-soluble solvent having an SP value of 24 (J/cm 3 ) 1/2 or more and a boiling point of 150° C. to 250° C. examples include polyhydric alcohols having 2 to 8 carbon atoms and polyalkylene glycols.
  • Polyhydric alcohols with 2 to 8 carbon atoms include 1,2-ethanediol (SP value: 30.3, boiling point: 197°C), 1,2-propanediol (SP value: 28.0, boiling point: 188°C), 1,3-propanediol (SP value: 32.9, boiling point: 213°C), 1,2-butanediol (SP value: 26.1, boiling point: 192°C), 1,3-butanediol (SP value: 30.3, boiling point: 207°C), 1,4-butanediol (SP value: 30.7, boiling point: 230°C), and 2,3-butanediol (SP value: 29.9, boiling point: 177°C), 2-methyl-1,3-propanediol (SP value: 30.3, boiling point: 214°C), 1,2-pentanediol (SP value: 25.0, boiling point: 210°C), 1,5-pentanediol (SP value
  • polyalkylene glycols examples include diethylene glycol (SP value: 30.6, boiling point: 244°C) and dipropylene glycol (SP value: 27.2, boiling point: 230°C).
  • the treatment solution may contain one or a combination of two or more of these water-soluble solvents.
  • the ink may contain at least one water-soluble solvent with a boiling point of 150°C to 250°C, and may also contain alcohols other than those mentioned above, polyhydric alcohols, amines, amides, glycol ethers, and 1,2-alkanediols with 4 or more carbon atoms.
  • solvents other than water-soluble solvents with a boiling point of 150°C to 250°C include glycerin (SP value: 33.5, boiling point: 290°C), trimethylolpropane (SP value: 32.5, boiling point: 295°C), triethylene glycol (SP value: 27.8, boiling point: 287°C), and tetraethylene glycol (SP value: 26.1, boiling point: 275°C).
  • the total content of the water-soluble solvent is preferably within the range of 5 to 40% by mass, and more preferably within the range of 10 to 40% by mass, relative to 100% by mass of the total mass of the treatment liquid.
  • the surfactant contained in the treatment liquid according to the present invention can improve the ejection stability of the treatment liquid from the nozzle, and can control the spread of droplets that have landed on a recording medium (enlargement of the dot diameter).
  • the surfactant is not particularly limited, but when an anionic compound is contained in other constituents of the ink, the ionicity of the surfactant is preferably anionic, nonionic or betaine type.
  • fluorine-based or silicone-based surfactants having high static surface tension reducing ability preferably, fluorine-based or silicone-based surfactants having high static surface tension reducing ability, anionic surfactants such as dioctyl sulfosuccinate having high dynamic surface tension reducing ability, and nonionic surfactants such as relatively low molecular weight polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, acetylene glycols, Pluronic surfactants (Pluronic is a registered trademark), and sorbitan derivatives are preferably used.
  • a fluorine-based or silicone-based surfactant in combination with a surfactant having high dynamic surface tension reducing ability.
  • An example of the polyoxyethylene alkyl ether is TRITON HW-1000 (TRITON is a registered trademark) manufactured by The Dow Chemical Company.
  • the silicone-based surfactant is preferably a polyether-modified silicone.
  • siloxanes having alkylene oxide groups at the side chain and/or both ends of the polydimethylsiloxane chain are included. Specific examples include BYK-331, BYK-333, BYK-345, BYK-3450, BYK-3451, BYK-3455, BYK-346, BYK-347, BYK-348, and BYK-349 manufactured by BYK-Chemie, and TEGOWetKL245, TEGOWet250, TEGOWet260, TEGOWet270, and TEGOWet2 manufactured by Evonik.
  • a trisiloxane having alkylene oxide groups at the side chain and/or at both ends of the polydimethylsiloxane chain is particularly preferred.
  • the trisiloxane preferably has a structure represented by the following general formula (1).
  • EO represents a repeating unit structure of polyethylene oxide, that is, a structure in which ethylene oxide, which is a three-membered cyclic ether, is opened.
  • PO represents a repeating unit structure of polypropylene oxide, that is, a structure in which propylene oxide, which is a three-membered cyclic ether, is opened.
  • the phrase "the order of [EO]m and [PO]n may be either” means that in the compound molecule represented by general formula (1), the order of the bonding positions to the parent siloxane skeleton may be changed as appropriate.
  • X is preferably an alkylene group having 3 carbon atoms (that is, a propylene group).
  • m is an integer of 5 to 20 and n is an integer of 0 to 6.
  • silicone surfactants having a structure represented by the general formula (1) are shown below as S-1 to S-8, but the invention is not limited thereto.
  • Examples of the trisiloxane include BYK-3450 and BYK-3451 manufactured by BYK Japan, and TEGOWET-KL245, TEGOWET-250, and TEGOWET-260 manufactured by Evonik.
  • the content of the polyether-modified silicone is preferably within a range of 0.5 to 2 mass %, and more preferably within a range of 0.5 to 1.5 mass %, relative to 100 mass % of the total mass of the treatment liquid.
  • fluorosurfactants refer to surfactants in which the hydrogen atoms bonded to the carbon of the hydrophobic group of a normal surfactant have been partially or entirely replaced with fluorine.
  • those having a perfluoroalkyl group in the molecule are preferred.
  • the treatment liquid according to the present invention contains a surfactant that is not contained in the ink, which will be described later, in the treatment liquid, and the following two patterns can be mentioned.
  • the surfactant contained in the ink is defined as surfactant S1
  • the surfactant contained in the treatment liquid is preferably a surfactant S2 which is different from the surfactant S1 contained in the ink.
  • the surfactant contained in the treatment liquid preferably contains the surfactant S2 in addition to the surfactant S1.
  • preferred combinations of surfactants include a surfactant contained in the treatment liquid that is a polyether-modified silicone, a trisiloxane-based surfactant, etc., and a surfactant contained in the ink that is a acetylene glycol-based surfactant, etc., and a polyether-modified silicone, etc.
  • a surfactant that is not contained in the ink i.e., a surfactant that destabilizes the dispersion stability of the ink
  • the amount of surfactant contained in the treatment liquid is not particularly limited, but is preferably within the range of 0.1 to 5.0% by mass of the total mass of the treatment liquid. It is more preferably within the range of 0.1 to 2.0% by mass.
  • the treatment liquid according to the present invention may contain water, and there is no particular limitation on the type of water that can be used. For example, ion-exchanged water, distilled water, or pure water can be used.
  • the treatment solution may contain other ingredients such as crosslinking agents, antifungal agents, and bactericides as appropriate, provided that the effects of the present invention are not impaired.
  • It can also contain various known additives such as various cationic or nonionic surfactants, fluorescent brighteners described in JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-242871, and JP-A-4-219266, antifoaming agents, lubricants such as diethylene glycol, preservatives, thickeners, antistatic agents, etc.
  • a treatment liquid layer by applying the treatment liquid according to the present invention as a coating liquid directly onto a substrate and drying it.
  • the inkjet method is used to apply the treatment liquid.
  • the ink according to the present invention contains at least a pigment and a resin, and preferably contains a water-soluble solvent, a surfactant, a wax and water.
  • an anionic dispersed pigment for example, a self-dispersed pigment having an anionic group on the surface, a pigment dispersed with an anionic polymer dispersant, or a pigment dispersed with the surface coated with an anionic resin.
  • a pigment dispersed with an anionic polymer dispersant since this has excellent dispersibility and reacts appropriately with the treatment liquid to provide pinning.
  • any conventionally known pigment can be used without any particular restrictions.
  • organic pigments such as insoluble pigments and lake pigments, and inorganic pigments such as titanium oxide can be preferably used.
  • the present invention is particularly effective in preventing bleeding and improving adhesion.
  • Titanium oxide has three crystal forms: anatase, rutile, and brookite, but the most commonly used are broadly classified as anatase and rutile. Although not particularly limited, rutile is preferred, as it has a high refractive index and high hiding power. Specific examples include the TR series from Fuji Titanium Industry Co., Ltd., the JR series from Teika Corporation, and Typeque from Ishihara Sangyo Co., Ltd.
  • the insoluble pigment is not particularly limited, but examples thereof include azo, azomethine, methine, diphenylmethane, triphenylmethane, quinacridone, anthraquinone, perylene, indigo, quinophthalone, isoindolinone, isoindoline, azine, oxazine, thiazine, dioxazine, thiazole, phthalocyanine, diketopyrrolopyrrole, etc.
  • organic pigments that can be preferably used include the following pigments.
  • pigments for magenta or red include C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 48:1, C.I. Pigment Red 53:1, C.I. Pigment Red 57:1, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 139, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I.
  • the pigments include C.I. Pigment Red 178, C.I. Pigment Red 202, C.I. Pigment Red 222, C.I. Pigment Violet 19, and the like.
  • orange or yellow pigments examples include C.I. Pigment Orange 31, C.I. Pigment Orange 43, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 15, C.I. Pigment Yellow 15:3, C.I. Pigment Yellow 17, C.I. Pigment Yellow 74, C.I. Pigment Yellow 93, C.I. Pigment Yellow 128, C.I. Pigment Yellow 94, C.I. Pigment Yellow 138, and C.I. Pigment Yellow 155.
  • C.I. Pigment Yellow 155 is preferred in terms of the balance between color tone and light resistance.
  • pigments for green or cyan examples include C.I. Pigment Blue 15, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 16, C.I. Pigment Blue 60, and C.I. Pigment Green 7.
  • black pigments examples include C.I. Pigment Black 1, C.I. Pigment Black 6, and C.I. Pigment Black 7.
  • the ink according to the present invention preferably contains a pigment dispersant for dispersing the pigment.
  • the pigment dispersant is not particularly limited, but is preferably a polymer dispersant having an anionic group, and one having a molecular weight in the range of 5,000 to 200,000 can be suitably used.
  • polymeric dispersants include block copolymers and random copolymers having a structure derived from two or more monomers selected from styrene, styrene derivatives, vinylnaphthalene derivatives, acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, and fumaric acid derivatives, as well as salts thereof, polyoxyalkylenes, and polyoxyalkylene alkyl ethers.
  • the polymer dispersant preferably has an acryloyl group and is preferably neutralized with a neutralizing base before addition.
  • the neutralizing base is not particularly limited, but is preferably an organic base such as ammonia, monoethanolamine, diethanolamine, triethanolamine, or morpholine.
  • the pigment is titanium oxide
  • the titanium oxide is preferably dispersed with a polymer dispersant having an acryloyl group.
  • the amount of polymer dispersant added is preferably within the range of 10 to 100% by mass, and more preferably within the range of 10 to 40% by mass, relative to the pigment.
  • the pigment has the form of a so-called capsule pigment, in which the pigment is coated with the polymer dispersant.
  • Various known methods can be used to coat the pigment with the polymer dispersant, but preferred examples include the phase inversion emulsification method, the acid precipitation method, and a method in which the pigment is dispersed in a polymerizable surfactant, a monomer is supplied thereto, and the pigment is coated while being polymerized.
  • a particularly preferred method is to dissolve the water-insoluble resin in an organic solvent such as methyl ethyl ketone, partially or completely neutralize the acidic groups in the resin with a base, add the pigment and ion-exchanged water, disperse the pigment, remove the organic solvent, and add water as necessary to prepare the pigment.
  • organic solvent such as methyl ethyl ketone
  • the average particle size of the pigment particles in the dispersed state in the ink is preferably within a range of 40 to 200 nm, and more preferably within a range of 50 to 100 nm, thereby improving the dispersion stability of the pigment and the storage stability of the ink.
  • the particle size of the pigment can be measured by a commercially available particle size measuring device using a dynamic light scattering method, an electrophoretic method, etc. In particular, the measurement by the dynamic light scattering method is simple and can measure the particle size range with high accuracy.
  • the pigment can be dispersed using a dispersing machine together with a dispersant and other additives required for the desired purpose.
  • a conventionally known ball mill, sand mill, line mill, high-pressure homogenizer, etc. can be used.
  • dispersing the pigment with a sand mill is preferable because it produces a sharp particle size distribution.
  • the material of the beads used for sand mill dispersion but from the viewpoint of preventing the generation of bead fragments and contamination of ionic components, it is preferable for the beads to be zirconia or zircon.
  • the bead diameter to be within the range of 0.3 to 3 mm.
  • the pigment content in the ink there are no particular limitations on the pigment content in the ink, but for titanium oxide, the preferred range is 7-18% by mass, and for organic pigments, the preferred range is 0.5-7% by mass.
  • the resin contained in the ink according to the present invention contains at least a polyolefin resin.
  • the polyolefin resin that can be used include polyethylene, polypropylene, ethylene-propylene copolymers, random copolymers or block copolymers (e.g., ethylene-propylene-butene copolymers) of ethylene and/or propylene with other comonomers (e.g., 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, ⁇ -olefin comonomers having 2 to 6 carbon atoms). Also usable are copolymers of two or more of the other comonomers and mixtures of two or more of the above polymers.
  • the polyolefin resin may be a commercially available product.
  • Examples of commercially available polyolefin resins include Arrowbase SB-1200 (manufactured by Unitika Ltd., "Arrowbase” is a registered trademark of the company), Auroren 150A, Auroren AE-301 (manufactured by Nippon Paper Industries Co., Ltd., "Auroren” is a registered trademark of the company), Superclone E-415 (manufactured by Nippon Paper Industries Co., Ltd., "Superclone” is a registered trademark of the company), and Hardlen Na-1001 (manufactured by Toyobo Co., Ltd., "Hardlen” is a registered trademark of the company).
  • an acid-modified polyolefin resin is preferred in terms of excellent character reproducibility in a two-liquid ink-jet recording method.
  • the acid-modified polyolefin resin is a resin obtained by modifying a polyolefin resin such as polyethylene or polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc.
  • a polyolefin resin modified with maleic anhydride it is preferable to use a polyolefin resin modified with maleic anhydride.
  • the polyolefin resin contains polyolefin resin particles having an average particle size in the range of 10 to 80 nm and polyolefin resin particles having an average particle size in the range of 100 to 300 nm.
  • the polyolefin resin particles having an average particle diameter of 10 to 80 nm are also referred to as small-diameter polyolefin resin particles
  • the polyolefin resin particles having an average particle diameter of 100 to 300 nm are also referred to as large-diameter polyolefin resin particles.
  • the ratio of the content (mass%) of the small-diameter polyolefin resin particles to the large-diameter polyolefin resin particles in the polyolefin resin is preferably within the range of 10:90 to 90:10, more preferably within the range of 30:70 to 70:30, and particularly preferably 50:50.
  • the average particle size of the polyolefin resin particles can be measured using a commercially available particle size measuring device that uses a dynamic light scattering method, electrophoresis method, or the like.
  • measurement using the dynamic light scattering method is simple and can accurately measure the particle size range.
  • the content of the polyolefin resin in the ink is preferably within a range of 1 to 15% by mass.
  • the resin according to the present invention preferably contains large-diameter polyolefin resin particles and small-diameter polyolefin resin particles, but is not limited thereto.
  • the resin according to the present invention may contain, for example, small-diameter polyolefin resin particles and other large-diameter (average particle diameter of 100 to 300 nm) resin particles. Examples of other resin particles include acrylic resin particles, polyester resin particles, polyurethane resin particles, etc., with acrylic resin particles being preferred.
  • acrylic resin commercially available products can be used.
  • examples of commercially available products include NeoCryl A-1127 manufactured by Kusumoto Chemicals Co., Ltd., Mowinyl 6899D, 6969D, 6800, and 6810 manufactured by Japan Coating Resins Co., Ltd., and TOCRYL W-7146, W-7150, and W-7152 manufactured by Toyochem Co., Ltd.
  • the water-soluble solvent contained in the ink according to the present invention is preferably a water-soluble solvent having a boiling point within the range of 150 to 250°C.
  • water-soluble solvents include alcohols, polyhydric alcohols, amines, amides, glycol ethers, 1,2-alkanediols having 4 or more carbon atoms, and the like, including those exemplified in the treatment liquid.
  • the ink may contain one or a combination of two or more of the water-soluble solvents listed above.
  • the amount of water-soluble solvent in the ink is not particularly limited, but is preferably within the range of 10 to 60% by mass.
  • ⁇ Surfactant> By incorporating a surfactant in the ink according to the present invention, it is possible to improve the ink ejection stability and control the spread (dot diameter) of the ink droplets that have landed on the recording medium.
  • the surfactants that can be used in the ink according to the present invention, but any of the surfactants exemplified in the treatment liquid can be used as long as they do not adversely affect the storage stability of the ink.
  • the treatment liquid does not contain the same surfactant as that contained in the ink.
  • the amount of surfactant contained in the ink is not particularly limited, but should be sufficient so long as it does not impair the storage stability of the ink, and is preferably within the range of 0.1 to 5.0% by mass. More preferably, it is within the range of 0.1 to 2.0% by mass.
  • the water contained in the ink according to the present invention is not particularly limited, and may be ion-exchanged water, distilled water, or pure water.
  • the wax contained in the ink according to the present invention is preferably a polyolefin wax.
  • the ink contains a polyolefin wax, the water resistance and abrasion resistance of the resulting recorded matter are improved.
  • the polyolefin wax is not particularly limited, and examples thereof include waxes and copolymers thereof made from olefins such as ethylene, propylene, butylene, or derivatives thereof, specifically polyethylene-based waxes, polypropylene-based waxes, polybutylene-based waxes, etc.
  • polyethylene-based waxes are preferred from the viewpoint of more effectively reducing the occurrence of cracks in images.
  • the polyolefin waxes can be used alone or in combination of two or more kinds.
  • the polyolefin wax is preferably used in the form of a polyolefin wax emulsion in which solid wax particles are dispersed in water using the surfactant described above.
  • polyethylene wax emulsion As an example of a polyolefin wax emulsion, a method for producing a polyethylene wax emulsion is given below.
  • Polyethylene wax is produced by polymerizing ethylene, synthesizing it from a hydrocarbon compound, or producing it by pyrolyzing polyethylene for general molding to reduce its molecular weight. This polyethylene wax is then oxidized to add carboxyl groups and hydroxyl groups. It is then emulsified using a surfactant to obtain a polyethylene wax emulsion in the form of an aqueous wax emulsion with excellent stability.
  • polyolefin waxes include the Chemipearl series, such as "Chemipearl W4005" (manufactured by Mitsui Chemicals, Inc., polyethylene wax, particle size 200 to 800 nm, ring and ball softening point 110°C, needle penetration hardness 3, solids content 40%).
  • AQUACER series such as AQUACER 513 (polyethylene wax, particle size 100 to 200 nm, melting point 130° C., solid content 30%), AQUACER 497, AQUACER 513, and AQUACER 517 (all manufactured by BYK Additives &Instruments); the Hi-Tech series, such as Hi-Tech E-7025P, Hi-Tech E-2213, Hi-Tech E-9460, Hi-Tech E-9015, Hi-Tech E-4A, Hi-Tech E-5403P, and Hi-Tech E-8237 (all manufactured by Toho Chemical Industry Co., Ltd.); and Nopcoat PEM-17 (manufactured by San Nopco Ltd., polyethylene emulsion, particle size 40 nm). These are commercially available in the form of an aqueous emulsion in which polyolefin wax is dispersed in water by a conventional method, and therefore can be added directly to the ink in the form of an aqueous emulsion
  • the ink used in the present invention may contain various known additives, such as polysaccharides, viscosity modifiers, resistivity modifiers, film-forming agents, UV absorbers, antioxidants, anti-fading agents, anti-mold agents, and anti-rust agents, as necessary, for the purpose of improving ejection stability, print head and ink cartridge compatibility, storage stability, image storage stability, and other performances.
  • additives such as polysaccharides, viscosity modifiers, resistivity modifiers, film-forming agents, UV absorbers, antioxidants, anti-fading agents, anti-mold agents, and anti-rust agents, as necessary, for the purpose of improving ejection stability, print head and ink cartridge compatibility, storage stability, image storage stability, and other performances.
  • liquid paraffin, dioctyl phthalate, tricresyl phosphate, silicone oil, and other oil droplet fine particles, and the like, as disclosed in JP-A-57-72555 may be used.
  • agents include ultraviolet absorbers described in JP-A-4193, JP-A-57-87988, and JP-A-62-261476, anti-fading agents described in JP-A-57-74192, JP-A-57-87989, JP-A-60-72785, JP-A-61-146591, JP-A-1-95091, and JP-A-3-13376, and fluorescent brighteners described in JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-242871, and JP-A-4-219266.
  • the ink used in the present invention having the above composition preferably has a viscosity of 1 to 40 mPa ⁇ s at 25°C, and more preferably 2 to 10 mPa ⁇ s.
  • the inkjet recording method of the present invention an image is formed by applying an ink set containing the above-mentioned treatment liquid and ink to the surface of a recording medium by a droplet ejection means and combining the inks.
  • the inkjet recording method of the present invention is a so-called two-liquid recording method.
  • this recording method for example, it is possible to continuously and efficiently apply the treatment liquid to the surface of a substrate (recording medium) and print with the ink using a single inkjet printer.
  • the treatment liquid and the ink can be unified on the substrate, and the variation in dot diameter between substrates is reduced. As a result, it is possible to print characters, patterns, and the like with excellent image quality.
  • the inkjet recording method includes a treatment liquid applying step and an ink applying step.
  • the treatment liquid application step is a step of applying a treatment liquid to the recording area of the substrate.
  • the ink application step is a step of applying ink, in a state where the ink is wet with the treatment liquid, to the area to which the treatment liquid has been applied in the treatment liquid application step, by an ink jet recording method.
  • the inkjet recording method of the present invention preferably includes an ink heating and drying step.
  • the ink heating and drying step is a step in which the treatment liquid and ink applied onto the substrate after the ink application step are heated and dried to form an image (image layer).
  • ink application process it is preferable to apply ink to the area to which the treatment liquid has been applied when the drying rate of the treatment liquid is 30% or less. It is also preferable to carry out the ink application process within 10 seconds after the treatment liquid application process. In particular, it is preferable to carry out the ink application process within 0.1 to 5 seconds after the treatment liquid application process when the drying rate of the treatment liquid is within the range of 1 to 10%.
  • the substrate (recording medium) applicable to the ink jet recording method of the present invention is a non-absorbent substrate made of a non-absorbent material.
  • non-absorbent recording substrate refers to a recording substrate (medium) that has a water absorption of 10 mL/ m2 or less from the start of contact to 30 msec in the Bristow method. Details of the test method are described, for example, in Standard No. 51 "Paper and paperboard - Liquid absorbency test method - Bristow method" of "JAPAN TAPPI Paper and Pulp Test Method 2000 Edition.”
  • a known plastic film can be used as the non-absorbent substrate.
  • plastic films include polyester films such as polyethylene terephthalate, polyethylene films, polypropylene films, polyamide films such as nylon, polystyrene films, polyvinyl chloride films, polycarbonate films, polyacrylonitrile films, and biodegradable films such as polylactic acid films.
  • polyester films such as polyethylene terephthalate, polyethylene films, polypropylene films, polyamide films such as nylon, polystyrene films, polyvinyl chloride films, polycarbonate films, polyacrylonitrile films, and biodegradable films such as polylactic acid films.
  • polyvinylidene chloride in order to impart gas barrier properties, moisture resistance, aroma retention, etc.
  • a film on which a metal oxide is vapor-deposited can also be preferably used.
  • the non-absorbent film either an unstretched film or a stretched film can be preferably used.
  • the thickness of the substrate is preferably within a range of 10 to 120 ⁇ m, more preferably 12 to 60 ⁇ m.
  • metal substrates such as tinplate for three-piece cans and tin-free steel plates (TFS plates, thickness 0.1 to 0.6 ⁇ m) are also preferably used as non-absorbent substrates.
  • they can be suitably used as packaging materials for canned foods having a coating layer of a thermosetting resin.
  • packaging materials for canned foods for example, the following materials are generally used to block air, moisture, and light and seal the food inside: Epoxy-phenolic paints and polyester laminating agents are used on the food side, and polyester or acrylic thermosetting paints are used on the outside.
  • the treatment liquid is applied onto a recording medium, which is a substrate.
  • the method for applying the treatment liquid onto the recording medium is the ink-jet method.
  • the substrate to be used is a metal substrate
  • a flatbed type printer to which the substrate is fixed for forming the treatment liquid layer.
  • the amount of treatment liquid applied per unit area on which an image is formed is preferably 5.0 g/ m2 or less. In particular, it is preferably within the range of 0.3 to 5.0 g/ m2 . This allows high character reproducibility to be obtained in a two-liquid inkjet recording method.
  • the ink application step is a step of applying the ink of the ink set by the inkjet method simultaneously with or immediately after applying the treatment liquid onto the recording medium, which is the substrate.
  • the drying rate of the treatment liquid is defined by the following formula.
  • the time between the application of the treatment liquid and the application of the ink can be adjusted, or the temperature of the recording medium can be appropriately adjusted.
  • the amount of ink droplets it is preferable to adjust the amount of ink droplets so that the amount of ink applied (also called the "application amount") per unit area is within the range of 2 to 25 times the amount of treatment liquid applied, in order to achieve higher image quality, and a more preferable range for the application amount is 2.5 to 3.5 times.
  • the inkjet method is not particularly limited, and a printer equipped with an inkjet head loaded with ink can be used. Specifically, ink is ejected as droplets from the nozzles of the inkjet head based on a digital signal, and these are then deposited on the treatment liquid layer of the substrate to perform printing.
  • the inkjet head may be either an on-demand type or a continuous type.
  • on-demand type inkjet heads include electro-mechanical conversion types, including single cavity type, double cavity type, bender type, piston type, shear mode type, and shared wall type, as well as electro-thermal conversion types, including thermal inkjet type and bubble jet type ("Bubble Jet” is a registered trademark of Canon Inc.).
  • an inkjet head that uses a piezoelectric element as the electromechanical conversion element used in the electromechanical conversion method (also called a piezo-type inkjet head).
  • the inkjet printer may use either a scanning type or a single-pass type inkjet head.
  • a single-pass type it is preferable to use a line head type inkjet head.
  • the line head type inkjet head refers to an inkjet head that has a length equal to or greater than the width of the printing range.
  • a single head that is equal to or greater than the width of the printing range may be used.
  • a combination of multiple heads may be used to form a head that is equal to or greater than the width of the printing range.
  • a plurality of heads may be arranged in parallel so that the nozzles are arranged in a staggered arrangement, thereby increasing the resolution of the heads as a whole.
  • the transport speed of the recording medium, which is the substrate can be set within a range of, for example, 1 to 120 m/min.
  • the faster the transport speed the faster the image formation speed.
  • the ink applied to the recording medium which is a base material, i.e., the area to which the ink is applied, is heated, thereby drying the ink and the treatment liquid.
  • the heating temperature of the area where the ink has been applied is preferably within the range of 60 to 200°C.
  • the ink heating time is adjusted appropriately according to the type of recording medium and the amount of ink applied.
  • the solvent components of the treatment liquid and ink such as water and water-soluble solvents, are removed.
  • the polyvalent metal salt is dried at a temperature above its thermal decomposition temperature, particularly in the case of metal substrates, and thermally decomposed. This also improves the abrasion resistance of the image and its adhesion to the substrate.
  • the heat drying may be performed using a non-contact heating type drying device such as a drying oven or a hot air blower, or a contact heating type drying device such as a hot plate or a heat roller.
  • the drying temperature can be obtained by measuring any one of the following throughout the entire drying period of the treatment liquid: (a) when a non-contact heating type drying device such as a drying oven or a hot air blower is used, the temperature of the oven or the hot air temperature, (b) when a contact heating type drying device such as a hot plate or a hot roller is used, the temperature of the contact heating part, or (c) the surface temperature of the surface to be dried.
  • a non-contact heating type drying device such as a drying oven or a hot air blower
  • a contact heating type drying device such as a hot plate or a hot roller
  • the surface temperature of the surface to be dried As for the measurement location, it is more preferable to measure the surface temperature of the surface to be dried (c).
  • the thickness of the image layer obtained in the above manner is preferably within the range of 0.3 to 3.0 ⁇ m, and more preferably within the range of 0.3 to 2.0 ⁇ m.
  • the thickness of the image layer is 0.3 ⁇ m or more, the adhesion and abrasion resistance of the image are easily improved.
  • the thickness of the image layer is 3.0 ⁇ m or less, the deformation stress applied to the image layer can be reduced, so the adhesion of the image layer is less likely to be impaired.
  • [Recording device] 2 is a schematic diagram of a recording apparatus that is preferred for the present invention, although the present invention is not limited to this.
  • the recording apparatus 1 is mainly composed of a treatment liquid application section 10 and an ink application section 20.
  • the treatment liquid application section 10 applies a treatment liquid onto the substrate F, and the ink application section 20 applies ink.
  • the treatment liquid application unit 10 is an inkjet head 11 capable of ejecting the treatment liquid onto the substrate.
  • the ink application section 20 is an inkjet head 21 capable of ejecting ink onto a substrate.
  • droplets 12 of the treatment liquid are ejected from the inkjet head 11 onto the substrate F fed from the feed roller 30, and a treatment liquid layer C is formed.
  • ink droplets 22 are ejected from an inkjet head 21 onto the treatment liquid layer C, and the treatment liquid and the ink are combined.
  • the drying section 23 heats and dries the area to which the ink has been applied, forming an image layer G.
  • the base material F on which the image layer G has been formed is wound up by the winding roller 40, thereby obtaining an image recorded matter.
  • FIG. 2 shows a case where the substrate F is a film substrate
  • the metal substrate in the case of a metal substrate or the like, can be placed on a conveyor belt, and the treatment liquid and ink can be applied in one pass while the belt is being conveyed.
  • the apparatus is configured to apply the ink after applying the treatment liquid onto the substrate, but the apparatus may be configured to apply the treatment liquid and the ink simultaneously.
  • the treatment liquid may be applied after the ink is applied and before the ink dries.
  • a flatbed type printer for applying the treatment liquid and ink.
  • the substrate is fixed, and the inkjet head can be moved in the main scanning direction and the sub-scanning direction that intersects with the main scanning direction. Therefore, printing can be performed without transporting the substrate.
  • Metal substrates such as tinplate cannot be transported from roll to roll like plastic film substrates, so it is preferable to use a flatbed type printer that does not require transporting the substrate. Examples of such flatbed type printers include the printers described in FIG. 1 of JP-A-2015-74161 and FIG. 1 of JP-A-2017-177578.
  • the image recorded matter according to the present invention has a substrate, and an image layer formed by applying a treatment liquid and an ink onto the substrate and combining them using the ink set.
  • the above-mentioned configuration shows the minimum configuration, and other functional layers may be formed between the substrate and the image layer.
  • a non-absorbent film substrate or the like may be attached to the upper layer of the image layer via, for example, a laminating adhesive layer.
  • a preferred configuration is one in which a first layer containing a thermosetting resin, an image layer containing the treatment liquid and ink, and a second layer containing a thermosetting resin are laminated in this order on a metal substrate.
  • Specific preferred examples of the image-recorded matter include packaging materials for packaging canned foods, retort foods, beverages, and the like.
  • FIG. 3 shows a cross-sectional view of a packaging material for canned foods, which is an example of the image recorded material of the present invention.
  • a thermosetting resin e.g., TW-1407 series, manufactured by T&K Toka
  • a thermosetting resin layer (base coat) 52 is roller-coated on a tinplate substrate 51 to form a thermosetting resin layer (base coat) 52.
  • An image layer 53 is formed thereon by combining a treatment liquid and an ink.
  • a thermosetting resin e.g., AX-10 series, manufactured by T&K Toka
  • the resulting product is heated and cured, and dried to obtain a packaging material 50 for canned foods.
  • Treatment Solution T1 4.0% by mass of calcium acetate hydrate as a flocculant, 28.0% by mass of propylene glycol and 5.0% by mass of 2-methyl-1,3-propanediol as solvents, 1.0% by mass of polyoxyethylene alkyl ether (TRITON HW-1000, manufactured by Dow Chemical Company) as a surfactant, 0.1% by mass of 1,2-benzisothiazolin-3-one (Proxel GXL(S), manufactured by SC Johnson Company) as a fungicide, and ion-exchanged water (balance; total amount was 100% by mass) were added with stirring. The resulting mixture was filtered through a 1 ⁇ m filter to obtain treatment liquid T1.
  • polyoxyethylene alkyl ether TRITON HW-1000, manufactured by Dow Chemical Company
  • 1,2-benzisothiazolin-3-one Proxel GXL(S), manufactured by SC Johnson Company
  • ion-exchanged water balance; total amount was 100% by mass
  • Treatment liquid T2 and T3 In preparing the treatment liquid T1, the types and amounts of the flocculant and surfactant were changed as shown in Tables I to VI below. Treatment liquids T2 and T3 were prepared in the same manner, except that the amount of ion-exchanged water added (the remainder) was also changed accordingly. Note that the solvent, antifungal agent, and ion-exchanged water are not listed in the tables below.
  • the dispersion conditions were changed so as to obtain the target average particle diameters (pigment particle diameters) shown in the following Tables I to VI, thereby obtaining dispersions of black pigment A and black pigment B.
  • the average particle size of the pigment particles contained in these pigment dispersions was 110 nm for the dispersion of black pigment A and 80 nm for the dispersion of black pigment B.
  • the average particle size was measured using a Zetasizer Nano S-90 manufactured by Marballoon Corporation.
  • ⁇ Preparation of Dispersion of Polyolefin Resin A> 100 g of a propylene-based random copolymer (propylene component 96 mol%, ethylene component 4 mol%, weight average molecular weight 100,000, Tm 125°C), 4 g of maleic anhydride, and 3 g of dicumyl peroxide were thoroughly mixed in advance. Then, the mixture was kneaded and reacted using a twin-screw extruder set at 180°C. Degassing was performed under reduced pressure in the extruder to remove remaining unreacted materials, and a maleic anhydride-modified polyolefin resin was obtained.
  • the resulting chlorinated polyolefin resin had a weight average molecular weight of 92,000, a graft mass of maleic anhydride of 3.5 mass %, a chlorine content of 15.5 mass %, and a melting point of 85°C.
  • a four-neck flask was equipped with a stirrer, a condenser, a thermometer, and a funnel.
  • 100 g of the obtained chlorinated modified polyolefin resin, 20 g of a surfactant (N,N-polyoxyalkylene-alkylamine), 18 g of 25% ammonia water (neutralizing agent), and 25 g of toluene were added to the four-neck flask, and kneaded at 120° C.
  • the average particle size of the resin in the obtained aqueous dispersion of the chlorinated modified polyolefin resin was 73 nm.
  • the aqueous dispersion of the chlorinated modified polyolefin resin obtained here is hereinafter referred to as a dispersion of polyolefin resin A.
  • a four-neck flask was equipped with a stirrer, a condenser, a thermometer, and a dropping funnel.
  • 13 g of maleic anhydride and 12 g of di-t-butyl peroxide as a radical generator were each added dropwise over a period of 2 hours while stirring the mixture, while maintaining the temperature of the system at 115° C.
  • the mixture was aged for 3 hours. After the reaction, the reaction mixture was cooled to room temperature and then poured into 20 L of acetone for purification to obtain a maleic anhydride graft copolymer (average molecular weight 18,500) having a graft amount of 2.1% by mass.
  • 100 g of the modified polyolefin resin obtained was placed in a reactor equipped with a stirrer, a thermometer, a cooling tube, and a dropping funnel, and heated to 120° C. to melt it. Thereafter, 6 g of morpholine was added as a basic substance while stirring, and further 40 g of polyethylene oxide was added as a surface active component.
  • the reaction conditions were changed so as to obtain the target average particle size (average particle size of the first or second resin) shown in Tables I to VI below, thereby obtaining a dispersion of polyolefin resin B and a dispersion of polyolefin resin C, respectively.
  • the average particle size of the resin particles contained in these resin dispersions was 78 nm for the dispersion of polyolefin resin B, and 108 nm for the dispersion of polyolefin resin C.
  • the average particle size was measured using a Zetasizer Nano S-90 manufactured by Marballoon Corporation.
  • Dispersion of Acrylic Resin D a commercially available product, NeoCryl A-1127 manufactured by Kusumoto Chemical Industries, Ltd., was used.
  • ⁇ Dynamic surface tension> The dynamic surface tension of the treatment liquid and ink prepared above was measured with a dynamic surface tensiometer (BP-100: manufactured by KRUSS) using the maximum bubble pressure method after a surface life of 50 msec. The measurement temperature was adjusted to 25° C.
  • the dynamic surface tensions (unit: mN/m) after a surface life of 50 msec are shown in Tables I to VI below.
  • the image with a resolution of 720 x 720 dpi was divided into two in each of the scanning direction X and the transport direction Y to create four images (180 x 180 dpi).
  • printing was performed in one direction, always with the treatment liquid being printed first.
  • the carriage transport speed was set to 300 mm/sec, and no drying process was provided between recording of the treatment liquid and the ink.
  • the printing test was performed in an environment of 25° C. and 50% RH.
  • the treatment liquid was applied in the amounts shown in Tables I to VI below at a maximum printing rate of 33% in accordance with the ink image area.
  • the ink was applied in a solid manner at a rate of 18 g/ m2 .
  • the time from when the treatment liquid was applied until when the ink was applied was measured and calculated to be 0.2 seconds.
  • the ink according to the present invention has superior storage stability compared to the ink of the comparative example. Furthermore, it is recognized that the ink set of the present invention is superior in character reproducibility and solid uniformity, and also has good adhesion, compared to the ink set of the comparative example.
  • the present invention can be used in an ink set and inkjet recording method that has good ink storage stability, high image quality, and good adhesion to non-absorbent substrates in a two-liquid inkjet recording system.

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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)
  • Chemical Kinetics & Catalysis (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
PCT/JP2023/034414 2022-10-19 2023-09-22 インクセット及びインクジェット記録方法 Ceased WO2024084890A1 (ja)

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EP23879538.9A EP4606872A4 (en) 2022-10-19 2023-09-22 INK SET AND INKJET PRINTING PROCESS

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JPS5787989A (en) 1980-11-21 1982-06-01 Matsushita Electric Ind Co Ltd Ink jet recording paper
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JPS5787989A (en) 1980-11-21 1982-06-01 Matsushita Electric Ind Co Ltd Ink jet recording paper
JPS5787988A (en) 1980-11-21 1982-06-01 Matsushita Electric Ind Co Ltd Ink jet recording paper
JPS5942993A (ja) 1982-09-03 1984-03-09 Canon Inc インクジエツト記録方法
JPS5952689A (ja) 1982-09-17 1984-03-27 Mitsubishi Paper Mills Ltd インクジェット記録用シート
JPS6072785A (ja) 1983-09-30 1985-04-24 Nippon Shokubai Kagaku Kogyo Co Ltd インクジェット記録用紙
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JPH0852867A (ja) 1994-08-10 1996-02-27 Canon Inc インクジェット記録装置
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JP2014024944A (ja) 2012-07-26 2014-02-06 Dic Corp インクジェット記録用水性インクセット
JP2015074161A (ja) 2013-10-09 2015-04-20 セイコーエプソン株式会社 印刷装置、印刷方法
JP2017177578A (ja) 2016-03-30 2017-10-05 ローランドディー．ジー．株式会社 プリンタおよび印刷用治具
JP2019218418A (ja) * 2018-06-15 2019-12-26 コニカミノルタ株式会社 インクジェット記録液セット及びインクジェット記録方法
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