WO2014045969A1 - Procédé d'enregistrement d'image - Google Patents

Procédé d'enregistrement d'image Download PDF

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Publication number
WO2014045969A1
WO2014045969A1 PCT/JP2013/074545 JP2013074545W WO2014045969A1 WO 2014045969 A1 WO2014045969 A1 WO 2014045969A1 JP 2013074545 W JP2013074545 W JP 2013074545W WO 2014045969 A1 WO2014045969 A1 WO 2014045969A1
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WIPO (PCT)
Prior art keywords
image
group
paper
meth
ink
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PCT/JP2013/074545
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English (en)
Japanese (ja)
Inventor
康史 大石
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富士フイルム株式会社
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Publication of WO2014045969A1 publication Critical patent/WO2014045969A1/fr

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    • 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
    • B41J11/00—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
    • B41J11/0015—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
    • B41J11/002—Curing or drying the ink on the copy materials, e.g. by heating or irradiating
    • B41J11/0021—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation
    • B41J11/00214—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation using UV radiation
    • 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
    • B41J29/00—Details of, or accessories for, typewriters or selective printing mechanisms not otherwise provided for
    • B41J29/377—Cooling or ventilating arrangements
    • 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
    • B41M5/0023—Digital printing methods characterised by the inks used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—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
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • 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
    • 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
    • B41J2002/012—Ink jet with intermediate transfer member

Definitions

  • the present invention relates to an image recording method using an inkjet method.
  • a method of forming an image by applying ink to a desired recording medium by an ink discharge head that discharges droplet-like ink is widely used.
  • image formation including a droplet discharge device, a fixing device, a cooling device for cooling the recording medium after fixing and heating, and a discharge unit for loading the recording medium
  • An apparatus is disclosed, and it is said that the occurrence of stacker blocking is suppressed (see, for example, JP 2012-135984 A).
  • an image recording process including an ink application process for forming an image by applying an ink composition containing a pigment and a polymer particle having a glass transition temperature of 70 ° C. or more, a drying process, and a curing process for curing the image.
  • a method see, for example, JP 2011-46872 A.
  • the image is cured to increase the image strength and prevent the image from being broken (blocked).
  • an inkjet recording apparatus that cools immediately after irradiation with ultraviolet rays is also disclosed (see, for example, Japanese Patent Application Laid-Open No. 2006-264264).
  • the appearance Since the image is a recorded matter, it is desirable that the appearance does not have an adhesive failure as described above, and that the appearance is not uneven.
  • adhesion failure of the image and gloss appearing as an appearance are one of important performances in terms of image quality.
  • stacker blocking is not prevented depending on the hue of the image or the amount of ink droplets, and colorants such as pigments aggregate locally. , Uneven gloss may occur.
  • the present invention has been made in view of the above, and it is an object of the present invention to provide an image recording method in which occurrence of stacker blocking and gloss unevenness is prevented when a large number of recording media are stacked in a paper discharge stacking unit. .
  • the drying process for drying the image, the curing process for curing the image by irradiating the dried image with active energy rays, and the image after curing are cooled so that the temperature difference before and after cooling is 15 ° C. or more.
  • An image recording method includes a cooling step and a stacking step of stacking and stacking a plurality of cooled recording media.
  • the cooling step is the image recording method according to ⁇ 1>, wherein the image is cooled to 60 ° C. or lower.
  • the polymer particle is a copolymer particle including at least one selected from the group consisting of a structural unit having an aromatic ring structure and a structural unit having an alicyclic structure. > Is an image recording method described in the above.
  • the polymer particles are particles of a copolymer including a structural unit derived from an aromatic group-containing (meth) acrylate monomer or a structural unit derived from an alicyclic (meth) acrylate. The image recording method according to any one of the above.
  • the polymer particle includes at least one selected from the group consisting of a structural unit having an aromatic ring structure and a structural unit having an alicyclic structure, and has a structural unit having an aromatic ring structure and an alicyclic structure.
  • the polymer particles have a copolymerization ratio of at least one of a structural unit derived from benzyl (meth) acrylate or a structural unit derived from phenoxyethyl (meth) acrylate, and (meth)
  • a structural unit derived from acrylic acid has a copolymerization ratio of 2% by mass to 30%
  • a structural unit derived from an alkyl (meth) acrylate having an alkyl moiety having 1 to 4 carbon atoms has a copolymerization ratio of 5% by mass to 90%.
  • a plurality of R 1 s each independently represent a hydrogen atom or a methyl group
  • a plurality of R 2 s each independently represent a linear or branched alkylene group having 2 to 4 carbon atoms.
  • R ⁇ 3 > represents a bivalent coupling group each independently.
  • k represents 2 or 3 each independently.
  • x, y, and z each independently represent an integer of 0 to 6, and x + y + z satisfies 0 to 18.
  • ⁇ 10> The image recording method according to any one of ⁇ 1> to ⁇ 9>, wherein the recording medium is a coated paper having a base paper and a coating layer containing an inorganic pigment.
  • the recording medium is a coated paper having a base paper and a coating layer containing an inorganic pigment.
  • the ink composition further contains a polymerization initiator.
  • ⁇ 12> The method according to any one of ⁇ 1> to ⁇ 11>, further including a treatment liquid application step of applying a treatment liquid containing an aggregation component that aggregates the components in the ink composition to the recording medium. This is an image recording method.
  • ⁇ 13> The image recording method according to ⁇ 12>, wherein the treatment liquid contains at least one selected from an acid, a polyvalent metal salt, and a cationic polymer.
  • the aggregation component is an acid.
  • the treatment liquid application step is provided before the ink application step.
  • an image recording method capable of preventing the occurrence of stacker blocking and gloss unevenness when a large number of recording media are stacked in a paper discharge stacking unit.
  • FIG. 1 is a configuration diagram illustrating a schematic configuration of a cooling device of an ink jet recording apparatus according to an embodiment of the present invention. It is a perspective view which shows the aspect which has arrange
  • the term “process” is not only included in an independent process, but is included in the term if the intended effect of this process is achieved even when it cannot be clearly distinguished from other processes.
  • numerical ranges indicated using “to” indicate ranges including numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition when there are a plurality of substances corresponding to each component in the composition, the plurality of substances present in the composition unless otherwise specified. Means the total amount.
  • (meth) acrylamide means acrylamide or methacrylamide
  • (meth) acrylic acid means acrylic acid or methacrylic acid
  • (meth) acrylate means acrylate or methacrylate. means.
  • an ink composition containing a colorant, water, a polymerizable compound, and polymer particles having a glass transition temperature (Tg) of 80 ° C. or higher and 150 ° C. or lower is applied to a recording medium by an ink jet method.
  • the image recording method of the present invention may further include other steps as necessary.
  • the ink When using a curable ink containing a polymerizable compound when recording an image by the inkjet method, the ink is cured, and unlike non-curable ink, stacker blocking between recording media when multiple sheets are stacked and accumulated And gloss unevenness were not expected.
  • image recording for commercial use when a large number of recording media (for example, 1000 sheets or more) are stacked and collected at high speed from the viewpoint of productivity, and heavy paper materials (for example, coated paper or paperboard) are coated.
  • the load applied to the recorded image tends to increase as compared with the conventional case.
  • the present inventors have found that even with a curable ink, stacker blocking and gloss unevenness occur, and as a result of intensive studies, the temperature of the image is changed using specific polymer particles. By (cooling), it has been possible to achieve both stacker blocking and prevention of gloss unevenness in the curable ink.
  • a curable ink composition containing a polymerizable compound is used, the Tg of the polymer particles is adjusted to a predetermined range, and the image after drying and curing is predetermined. Apply cooling.
  • the Tg of the polymer particles is set in a range in which image sticking is suppressed and the image is not easily brittle. Further, depending on the solvent content and the image temperature, image deformation due to resin components (change in contact area with the image) ) It is considered important to prevent easy-to-use situations by cooling.
  • the strength of the image portion can be maintained even when images are formed at a relatively high speed or on both sides, and the recording media are stacked in a state where the contact area with the adjacent recording media is large and the images are easily peeled off. Can be avoided.
  • the method of the present invention it is possible to effectively prevent the occurrence of stacker blocking and gloss unevenness between recording media on which a large number of sheets are stacked, and to provide a recorded matter with high image quality.
  • an ink composition containing a colorant, water, a polymerizable compound, and polymer particles having a glass transition temperature of 80 ° C. or higher and 150 ° C. or lower is applied to a recording medium by an ink jet method to record an image. It is a process.
  • the ink composition is ejected in the form of droplets on a recording medium to form an image.
  • the ink jet method for example, the method described in paragraph numbers 0093 to 0105 of JP-A No. 2003-306623 can be applied.
  • the inkjet method is not particularly limited, and is a known method, for example, a charge control method that ejects ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses vibration pressure of a piezoelectric element, Either an acoustic ink jet method that converts an electrical signal into an acoustic beam, irradiates the ink with ink and ejects the ink using radiation pressure, or a thermal ink jet method that heats the ink to form bubbles and uses the generated pressure It may be used.
  • a charge control method that ejects ink using electrostatic attraction
  • a drop-on-demand method pressure pulse method
  • a thermal ink jet method that heats the ink to form bubbles and uses the generated pressure It may be used.
  • Sho 54-59936 causes a sudden change in volume of the ink subjected to the action of thermal energy, and the ink is ejected from the nozzle by the action force caused by this state change.
  • Ink jet method can be used effectively.
  • the ink jet method includes a method for ejecting a large number of low-density inks called photo inks in a small volume, a method for improving image quality using a plurality of inks having substantially the same hue and different concentrations, and a colorless and transparent ink. The method using is included.
  • an image can be recorded by changing the conveyance speed of the recording medium.
  • the conveying speed is not particularly limited as long as the image quality is not impaired, and is preferably 100 to 3000 mm / s, more preferably 150 to 2700 mm / s, and further preferably 250 to 2500 mm / s. .
  • the conveying speed is within the above range, the effect of preventing the occurrence of stacker blocking and gloss unevenness that are likely to occur when an image is recorded at a relatively high speed is further exhibited.
  • the maximum application amount of the ink composition to the recording medium is preferably 15 ml / m 2 or less.
  • the maximum applied amount is 15 ml / m 2 or less, the adhesion of the image to the recording medium is more excellent.
  • the maximum application amount is more preferably 8 to 15 ml / m 2 from the viewpoint of the adhesion and density of the image to the recording medium.
  • the maximum application amount can be controlled by adjusting the discharge method from the discharge nozzle.
  • the recording medium in the present invention is not particularly limited.
  • general printing paper mainly composed of cellulose such as so-called high-quality paper, coated paper, and art paper, used for general offset printing can be used.
  • image recording by a general ink jet method using water-based ink is relatively slow in absorption and drying of ink, and color material movement is likely to occur after droplet ejection, resulting in poor image quality.
  • the image recording method of the present invention it is possible to record a high-quality image excellent in color density and hue by suppressing color material movement.
  • fine paper for example, “OK Prince fine quality” manufactured by Oji Paper Co., Ltd., “Shiorai” manufactured by Nippon Paper Industries Co., Ltd., “New NPI fine quality” manufactured by Nippon Paper Industries Co., Ltd.
  • Fine coated paper eg “OK Everlight Coat” manufactured by Oji Paper Co., Ltd.
  • coated paper used for general offset printing is preferable.
  • the coated paper is obtained by applying a coating material to the surface of a base paper such as high-quality paper or neutral paper, which is mainly composed of cellulose and is not generally surface-treated, and is provided with a coating layer.
  • the coated paper is liable to cause quality problems with respect to the glossiness and scratch resistance of the image when an ordinary aqueous ink is ejected by the ink jet method to record an image.
  • the image recording method of the present invention even when coated paper is used, an image in which the occurrence of stacker blocking due to gloss unevenness and texture when stacking a large number of recording media is stacked is suppressed. Obtainable.
  • a coated paper having a base paper and a coating layer containing an inorganic pigment from the viewpoint that the effect of preventing the stacker blocking caused by the gloss unevenness and the coating layer being destroyed appears, and the base paper and kaolin and More preferably, a coated paper having a coating layer containing calcium bicarbonate is used.
  • art paper, coated paper, lightweight coated paper, finely coated paper, or paperboard is more preferable.
  • the ink composition according to the present invention includes at least a colorant, water, a polymerizable compound, and polymer particles having a glass transition temperature of 80 ° C. or higher and 150 ° C. or lower, and further includes a water-soluble organic solvent and a surfactant as necessary. , Waxes, and / or other additives.
  • the ink composition in the invention contains at least one colorant.
  • the colorant known dyes, pigments and the like can be used without particular limitation. Among these, from the viewpoint of ink colorability, a colorant that is insoluble or hardly soluble in water is preferable, and examples thereof include various pigments, disperse dyes, oil-soluble dyes, and dyes that form J aggregates. As the colorant, a pigment is more preferable from the viewpoint of light resistance.
  • any of an organic pigment and an inorganic pigment may be sufficient.
  • organic pigments include azo pigments, polycyclic pigments, dye chelates, nitro pigments, nitroso pigments, and aniline black.
  • azo pigments and polycyclic pigments are more preferable.
  • the azo pigments include azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments.
  • polycyclic pigment examples include phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments.
  • dye chelates include basic dye chelates and acid dye chelates.
  • inorganic pigment examples include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black.
  • carbon black examples include those produced by known methods such as a contact method, a furnace method, and a thermal method.
  • the ink composition in the present invention may contain at least one dispersant.
  • a polymer dispersant or a low molecular surfactant type dispersant can be used as a pigment dispersant.
  • the polymer dispersant may be either a water-soluble dispersant or a water-insoluble dispersant.
  • the low molecular surfactant type dispersant can stably disperse the pigment in the aqueous solvent while keeping the ink at a low viscosity.
  • the low molecular surfactant type dispersant is a low molecular dispersant having a molecular weight of 2,000 or less.
  • the molecular weight of the low-molecular surfactant type dispersant is preferably 100 to 2,000, more preferably 200 to 2,000.
  • the low molecular surfactant type dispersant has a structure containing a hydrophilic group and a hydrophobic group. Further, it is sufficient that one or more hydrophilic groups and hydrophobic groups are independently contained in one molecule of a low-molecular-weight surfactant type dispersant, and plural kinds of hydrophilic groups and / or hydrophobic groups are used. It may have a group. In addition, the low-molecular-weight surfactant-type dispersant can appropriately have a linking group for linking a hydrophilic group and a hydrophobic group.
  • hydrophilic group examples include an anionic group, a cationic group, a nonionic group, and a betaine-type hydrophilic group combining these.
  • the anionic hydrophilic group may be any as long as it has a negative charge, but is a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, a sulfinic acid group, or a carboxylic acid group. It is preferably a phosphoric acid group or a carboxylic acid group, more preferably a carboxylic acid group.
  • the cationic hydrophilic group may be any one having a positive charge, but is preferably an organic cationic substituent, and more preferably a nitrogen or phosphorus cationic group. Further, it is more preferably a pyridinium cation or an ammonium cation.
  • the nonionic hydrophilic group include polyethylene oxide, polyglycerin, a part of a sugar unit, and the like.
  • the hydrophilic group is preferably an anionic hydrophilic group.
  • the anionic hydrophilic group is preferably a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, a sulfinic acid group, or a carboxylic acid group, and is a phosphoric acid group or a carboxylic acid group. It is more preferable that it is a carboxylic acid group.
  • the pKa of the low molecular surfactant type dispersant is from the viewpoint of promoting the aggregation reaction by contacting with an acidic treatment liquid. It is preferably 3 or more.
  • the low molecular surfactant type dispersant preferably has a carboxylic acid group as an anionic group.
  • hydrophobic group examples include groups having a hydrocarbon-based, fluorocarbon-based, or silicone-based structure, and hydrocarbon-based hydrophobic groups are particularly preferable.
  • the structure of the hydrophobic group may be either a linear structure or a branched structure.
  • the structure of the hydrophobic group may be a single chain structure or a chain structure of two or more chains, and in the case of a structure of two or more chains, it may have a plurality of types of hydrophobic groups.
  • the hydrophobic group is preferably a hydrocarbon group having 2 to 24 carbon atoms, more preferably a hydrocarbon group having 4 to 24 carbon atoms, and further preferably a hydrocarbon group having 6 to 20 carbon atoms.
  • examples of the water-soluble dispersant include hydrophilic polymer compounds.
  • hydrophilic polymer compounds there are plant polymers such as gum arabic, tragan gum, guar gum, karaya gum, locust bean gum, arabinogalactone, pectin, quince seed starch, seaweed-based high alginic acid, carrageenan, agar, etc.
  • examples include natural hydrophilic polymer compounds such as molecules, animal polymers such as gelatin, casein, albumin and collagen, and microbial polymers such as xanthene gum and dextran.
  • hydrophilic polymer compound examples include fibrous polymers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose, and starch polymers such as sodium starch glycolate and sodium starch phosphate. And hydrophilic polymer compounds modified with natural products such as seaweed polymers such as sodium alginate and propylene glycol alginate as raw materials. Furthermore, examples of the hydrophilic polymer compound include vinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl methyl ether, non-crosslinked polyacrylamide, polyacrylic acid or an alkali metal salt thereof, water-soluble styrene acrylic resin, and the like.
  • Acrylic resin water-soluble styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic acid resin, polyvinyl pyrrolidone, polyvinyl alcohol, alkali metal salts of ⁇ -naphthalene sulfonic acid formalin condensate, quaternary ammonium and amino
  • a synthetic hydrophilic polymer compound such as a polymer compound having a salt of a cationic functional group such as a group in the side chain and a natural polymer compound such as shellac.
  • water-soluble dispersants introduced with carboxyl groups such as copolymers of acrylic acid, methacrylic acid, or styrene acrylic acid with homopolymers and other monomers having hydrophilic groups are highly hydrophilic. Preferred as a molecular compound.
  • a polymer having both a hydrophobic part and a hydrophilic part can be used as the water-insoluble dispersant.
  • styrene- (meth) acrylic acid copolymer styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, (meth) acrylic acid ester- (meth) acrylic acid copolymer, polyethylene glycol ( Examples thereof include a (meth) acrylate- (meth) acrylic acid copolymer, a vinyl acetate-maleic acid copolymer, and a styrene-maleic acid copolymer.
  • the weight average molecular weight of the polymer dispersant is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 40,000, and particularly preferably 10,000. 000 to 40,000.
  • the polymer dispersant preferably contains a polymer having a carboxyl group from the viewpoints of self-dispersibility and aggregation rate when the treatment liquid comes into contact.
  • the polymer dispersant has a carboxyl group and has an acid value of 100 mgKOH / g or less.
  • a polymer having an acid value of 25 to 100 mgKOH / g is more preferable.
  • a polymer dispersant having a carboxyl group and an acid value of 25 to 100 mgKOH / g is effective. .
  • the processing liquid will be described later.
  • the mixing mass ratio (p: s) between the pigment (p) and the dispersant (s) is preferably in the range of 1: 0.06 to 1: 3, and in the range of 1: 0.125 to 1: 2. Is more preferable, and the range of 1: 0.125 to 1: 1.5 is more preferable.
  • a dye may be used instead of the pigment.
  • a dye held on a water-insoluble carrier can be used.
  • the carrier holding the dye water-insoluble colored particles
  • the dispersant the above-described dispersants can be suitably used.
  • the ink composition preferably includes a pigment and a dispersant, includes an organic pigment and a polymer dispersant, and at least a part of the pigment surface is polymer-dispersed. More preferably, it is contained as a water-dispersible pigment coated with an agent. Furthermore, it is particularly preferable that the ink composition includes an organic pigment and a polymer dispersant containing a carboxyl group, and a water-dispersible pigment in which at least a part of the pigment surface is coated with a polymer dispersant having a carboxyl group. From the viewpoint of cohesiveness, the pigment is preferably coated with a polymer dispersant containing a carboxyl group and is insoluble in water.
  • the average particle size of the pigment in the dispersed state is preferably 10 to 200 nm, more preferably 10 to 150 nm, and further preferably 10 to 100 nm.
  • the average particle size is 200 nm or less, the color reproducibility is good, and the droplet ejection characteristics when droplets are ejected by the ink jet method are good.
  • the average particle size is 10 nm or more, light resistance is improved.
  • the particle size distribution of the color material is not particularly limited, and may be either a wide particle size distribution or a monodisperse particle size distribution. Two or more color materials having a monodisperse particle size distribution may be mixed and used.
  • the average particle diameter of the pigment in the dispersed state indicates the average particle diameter in the ink state, but the same applies to the so-called concentrated ink dispersion in the previous stage before the ink is formed.
  • the average particle size and particle size distribution of the pigment in the dispersed state are measured by a dynamic light scattering method using a nanotrack particle size distribution measuring device UPA-EX150 (manufactured by Nikkiso Co., Ltd.). Is required.
  • One kind of colorant may be used alone, or a plurality of colorants may be selected from within each group or between each group and used in combination.
  • the content of the colorant in the ink composition is preferably 0.1 to 20% by mass, and preferably 0.2 to 15%, based on the total solid mass of the ink composition, from the viewpoints of colorability, storage stability, and the like. % By mass is more preferable, and 0.5 to 10% by mass is particularly preferable.
  • the ink composition in the invention contains at least one polymer particle having a glass transition temperature of 80 ° C. or higher and 150 ° C. or lower.
  • the polymer particles are particles that are dispersed and contained in the ink separately from the above-described polymer dispersant (a polymer dispersant covering at least a part of a pigment or the like).
  • the polymer particles When the polymer particles come into contact with a treatment liquid described later or a region where the polymer particles are dried, the polymer particles are dispersed and destabilized in the ink composition and aggregate to fix the ink composition by thickening the ink composition. It has a function, and can improve the adhesion of the ink composition to the recording medium and the scratch resistance of the image.
  • the polymer particles can be used, for example, as a latex in which a particulate polymer is dispersed in an aqueous medium.
  • Polymers include acrylic resins, vinyl acetate resins, styrene-butadiene resins, vinyl chloride resins, acrylic-styrene resins, butadiene resins, styrene resins, crosslinked acrylic resins, crosslinked styrene resins, benzoguanamine resins, A phenol resin, a silicone resin, an epoxy resin, a urethane resin, a paraffin resin, a fluorine resin, or the like can be used.
  • the aqueous medium contains water, and may contain a hydrophilic organic solvent as necessary.
  • an aqueous medium containing water and 0.2% by mass or less of a hydrophilic organic solvent with respect to water is preferable, and a medium composed only of water is more preferable.
  • the present invention by containing polymer particles having a glass transition temperature (Tg) of 80 ° C. or higher and 150 ° C. or lower, the occurrence of stacker blocking when collecting and collecting is suppressed, and uneven glossiness of the image is also suppressed.
  • Tg glass transition temperature
  • Tg glass transition temperature
  • Tg exceeds 150 ° C. the image becomes brittle and the image is destroyed when peeling off the image portion where the tackiness occurs, which causes stacker blocking.
  • the Tg of the polymer particles in the present invention is more preferably in the range of 90 ° C. or higher and 140 ° C. or lower, more preferably in the range of 100 ° C. or higher and 130 ° C. or lower, from the viewpoint of more effectively preventing the occurrence of stacker blocking and gloss unevenness.
  • the glass transition temperature (Tg) of the polymer particles can be appropriately controlled by a commonly used method.
  • the glass transition temperature (Tg) of the polymer particles is set to a desired range by appropriately selecting the type of monomer (polymerizable compound) constituting the polymer particles, the composition ratio thereof, the molecular weight of the polymer constituting the polymer particles, and the like. Can be controlled.
  • the measured Tg obtained by actual measurement is applied as the glass transition temperature (Tg) of the polymer particles.
  • the measurement Tg means a value measured under normal measurement conditions using a differential scanning calorimeter (DSC) EXSTAR 6220 manufactured by SII Nanotechnology.
  • DSC differential scanning calorimeter
  • calculation Tg calculated by the following calculation formula is applied.
  • the homopolymer glass transition temperature value (Tg i ) of each monomer is a value obtained from Polymer Handbook (3rd Edition) (by J. Brandrup, EH Immergut (Wiley-Interscience, 1989)). It is.
  • the polymer particles are polymer particles obtained by a phase inversion emulsification method, that is, synthesized in an organic solvent, neutralize part or all of anionic groups, and as a dispersion having water as a continuous phase.
  • the prepared particles are preferable, and the following self-dispersing polymer particles (self-dispersing polymer particles) are more preferable.
  • the self-dispersing polymer is dispersed in an aqueous medium by a functional group (particularly an acidic group or a salt thereof) possessed by the polymer itself when it is dispersed by a phase inversion emulsification method in the absence of a surfactant.
  • a water-insoluble polymer that can be in a state.
  • the dispersed state refers to an emulsified state (emulsion) in which a water-insoluble polymer is dispersed in an aqueous medium and a dispersed state (suspension) in which a water-insoluble polymer is dispersed in an aqueous medium. It includes both states.
  • Water-insoluble means that the amount dissolved in 100 parts by mass of water (25 ° C.) is 5.0 parts by mass or less.
  • phase inversion emulsification method for example, a polymer is dissolved or dispersed in a solvent (for example, a water-soluble organic solvent) and then poured into water as it is without adding a surfactant.
  • a solvent for example, a water-soluble organic solvent
  • examples include a method of obtaining an aqueous dispersion in an emulsified or dispersed state after stirring and mixing in a state in which a group (for example, an acidic group) is neutralized and removing the solvent.
  • self-dispersing polymer particles examples include self-dispersing polymer particles described in paragraphs 0090 to 0121 of JP2010-64480A and paragraphs 0130 to 0167 of JP2011-068805A. , Tg of 80 ° C. or higher and 150 ° C. or lower can be selected and used.
  • the polymer forming the polymer particles preferably has at least one of a structural unit having an aromatic ring structure (aromatic group) and a structural unit having an alicyclic structure (alicyclic group).
  • aromatic group aromatic group
  • alicyclic group alicyclic group
  • the strength (for example, scratch resistance and blocking resistance) of the formed image is further improved, and the deformation of the image when it is accumulated and loaded, that is, the image and the recording medium in contact with the image or other image
  • the increase in the contact area between the two is suppressed to be small, which is effective in suppressing the occurrence of stacker blocking.
  • Examples of the structural unit having an aromatic group include a structural unit having a phenyl group, a structural unit having a benzyl group, a structural unit having a phenoxy group, and a structural unit having a phenethyl group.
  • a structural unit having a benzyl group and a structural unit having a phenoxy group are preferable.
  • the structural unit having an aromatic group is preferably a structural unit derived from a monomer having an aromatic group (hereinafter also referred to as “aromatic group-containing monomer”).
  • the aromatic group-containing monomer is preferably a monomer having an aromatic group derived from an aromatic hydrocarbon and an ethylenically unsaturated bond.
  • the aromatic group-containing monomer may be used alone or in combination of two or more. Examples of the aromatic group-containing monomer include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, and a styrene monomer.
  • the aromatic group-containing monomer is preferably an aromatic group-containing (meth) acrylate monomer, such as phenoxyethyl (meth) acrylate, benzyl (meta ) Acrylate and phenyl (meth) acrylate are more preferable, and phenoxyethyl (meth) acrylate and benzyl (meth) acrylate are more preferable.
  • (Meth) acrylate” means acrylate or methacrylate.
  • the structural unit having an alicyclic group is preferably a structural unit derived from a monomer having an alicyclic group (hereinafter also referred to as “alicyclic group-containing monomer”).
  • the alicyclic group-containing monomer is preferably a monomer having an alicyclic group and an ethylenically unsaturated bond, and a (meth) acrylate having an alicyclic group (hereinafter referred to as “alicyclic (meth) acrylate”).
  • the alicyclic (meth) acrylate includes a structural site derived from (meth) acrylic acid and a structural site derived from alcohol, and the structural site derived from alcohol is unsubstituted or substituted. It has a structure containing at least one hydrogen group.
  • the alicyclic hydrocarbon group may be a structural site derived from alcohol itself, or may be bonded to a structural site derived from alcohol via a linking group.
  • the alicyclic hydrocarbon group is not particularly limited as long as it contains a cyclic non-aromatic hydrocarbon group, and is a monocyclic hydrocarbon group, a bicyclic hydrocarbon group, a tricyclic or more polycyclic group.
  • a hydrocarbon group is mentioned.
  • the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a cycloalkenyl group, a bicyclohexyl group, a norbornyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, and an adamantyl group.
  • the alicyclic hydrocarbon group may further have a substituent.
  • substituents include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, a hydroxyl group, a primary amino group, a secondary amino group, a tertiary amino group, an alkyl or arylcarbonyl group, and a cyano group. Is mentioned.
  • the alicyclic hydrocarbon group may further form a condensed ring.
  • the alicyclic hydrocarbon group in the present invention preferably has 5 to 20 carbon atoms in the alicyclic hydrocarbon group portion from the viewpoint of viscosity and solubility.
  • Monocyclic (meth) acrylates include cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, and cyclononyl.
  • Examples thereof include cycloalkyl (meth) acrylates having 3 to 10 carbon atoms in the cycloalkyl group such as (meth) acrylate and cyclodecyl (meth) acrylate.
  • Examples of the bicyclic (meth) acrylate include isobornyl (meth) acrylate and norbornyl (meth) acrylate.
  • Examples of the tricyclic (meth) acrylate include adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. These can be used alone or in admixture of two or more.
  • the alicyclic (meth) acrylates are bicyclic (meth) acrylates and tricyclic or more polycyclic rings. It is preferably at least one selected from the group consisting of formula (meth) acrylates, and more preferably a compound selected from isobornyl (meth) acrylate, adamantyl (meth) acrylate, and dicyclopentanyl (meth) acrylate.
  • the polymer particle is preferably a copolymer particle having a structural unit having an aromatic group or a structural unit having an alicyclic group, and further, a structural unit derived from an aromatic group-containing (meth) acrylate monomer or Copolymer particles containing a structural unit derived from an alicyclic (meth) acrylate are preferred.
  • the total ratio of the structural unit having an aromatic group and the structural unit having an alicyclic group in the polymer particle is preferably 5% by mass to 85% by mass, and more preferably 10% by mass to 75% by mass.
  • the Tg of the polymer particles can be easily adjusted to a range of 80 ° C. or higher and 150 ° C. or lower, and the stability of the self-emulsification or dispersion state of the polymer particles is improved.
  • polymer particles containing a structural unit having an aromatic group are more preferable.
  • the polymer particles preferably contain a hydrophilic structural unit from the viewpoint of dispersibility in the ink composition (in the case of self-dispersing polymer particles, self-dispersibility).
  • the hydrophilic structural unit is preferably a structural unit derived from a monomer having a hydrophilic group (hereinafter also referred to as “hydrophilic group-containing monomer”).
  • the hydrophilic structural unit may be derived from one type of hydrophilic group-containing monomer or may be derived from two or more types of hydrophilic group-containing monomers.
  • the hydrophilic group is not particularly limited, and may be a dissociable group or a nonionic hydrophilic group.
  • the hydrophilic group is preferably a dissociable group and more preferably an anionic dissociable group from the viewpoint of promoting self-dispersion of the polymer particles and the stability of the formed emulsified or dispersed state.
  • the dissociable group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Among them, a carboxyl group is preferable from the viewpoint of fixability when an ink composition is used.
  • the hydrophilic group-containing monomer is preferably a dissociable group-containing monomer from the viewpoint of self-dispersibility and aggregation of polymer particles, and is a dissociable group-containing monomer having a dissociable group and an ethylenically unsaturated bond. It is preferable.
  • the dissociable group-containing monomer include an unsaturated carboxylic acid monomer, an unsaturated sulfonic acid monomer, and an unsaturated phosphoric acid monomer.
  • the unsaturated carboxylic acid monomer examples include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxymethyl succinic acid.
  • Specific examples of the unsaturated sulfonic acid monomer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 3-sulfopropyl (meth) acrylate, bis- (3-sulfopropyl) -itaconate, and the like. Can be mentioned.
  • the unsaturated phosphoric acid monomer examples include vinyl phosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2- Examples include acryloyloxyethyl phosphate.
  • an unsaturated carboxylic acid monomer is preferable and (meth) acrylic acid is more preferable from the viewpoints of dispersion stability and ejection stability.
  • the content ratio of the hydrophilic structural unit in the polymer particles is not particularly limited, but is preferably 2% by mass to 30% by mass and 5% by mass to 20% by mass with respect to the total amount of the polymer particles from the viewpoint of dispersion stability. % Is more preferable, and 5% by mass to 15% by mass is particularly preferable.
  • the polymer particles preferably include a structural unit having an alkyl group from the viewpoint of flexibility of the polymer skeleton and ease of glass transition temperature (Tg) control.
  • the carbon number of the alkyl group in the structural unit having an alkyl group is preferably 1 to 4.
  • the structural unit having an alkyl group is preferably a structural unit derived from a monomer having an alkyl group (hereinafter also referred to as “alkyl group-containing monomer”).
  • alkyl group-containing monomer examples include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t -Alkyl (meth) acrylates such as butyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate; hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Ethylenically unsaturated monomers having a hydroxyl group such as 4-hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate; Dialkylaminoalkyl (
  • alkyl (meth) acrylate is preferable, alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms is more preferable, methyl (meth) acrylate or ethyl (meth) acrylate is more preferable, methyl (meth) acrylate Is particularly preferred.
  • the content ratio of the structural unit having an alkyl group in the polymer particles is not particularly limited, but from the viewpoint of dispersion stability, it is preferably 5% by mass to 90% by mass, and preferably 30% by mass to 80% by mass with respect to the total amount of the polymer particles.
  • the mass% is more preferable.
  • the polymer particles may contain structural units other than the above-described structural units as necessary.
  • the preferred form of the copolymerization ratio of the polymer forming the polymer particles is as follows from the viewpoint of easily adjusting the glass transition temperature to 80 ° C. or higher and 150 ° C. or lower and maintaining good dispersion stability. It is. That is, the preferred polymer particle form is 5% by mass to 60% by mass (particularly preferably 10% by mass to 55% by mass) as a copolymerization ratio of a structural unit having an aromatic group (preferably benzyl group or phenoxy group).
  • hydrophilic structural unit as a copolymerization ratio of 2% by mass to 30% by mass (more preferably 5% by mass to 20% by mass, particularly preferably 5% by mass to 15% by mass), and a structural unit having an alkyl group As a copolymerization ratio of 5 mass% to 90 mass% (more preferably 30 mass% to 80 mass%).
  • a particularly preferred form of the polymer particles is 5% by mass to 60% by mass (particularly preferably 10% by mass) with a copolymerization ratio of at least one of a structural unit derived from benzyl (meth) acrylate or a structural unit derived from phenoxyethyl (meth) acrylate.
  • the molecular weight range of the polymer forming the polymer particles is preferably 3000 to 200,000, more preferably 5000 to 150,000, and still more preferably 10,000 to 100,000 in terms of weight average molecular weight.
  • the weight average molecular weight By setting the weight average molecular weight to 3000 or more, the amount of water-soluble components can be effectively suppressed.
  • self-dispersion stability can be improved by making a weight average molecular weight into 200,000 or less.
  • the weight average molecular weight of the polymer constituting the polymer particles is measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • HLC-8020GPC manufactured by Tosoh Corporation
  • TSKgel Supermultipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) are used as columns
  • THF tetrahydrofuran
  • the conditions are as follows: the sample concentration is 0.45 mass%, the flow rate is 0.35 ml / min, the sample injection amount is 10 ⁇ l, the measurement temperature is 40 ° C., and the RI detector is used.
  • the calibration curves are standard samples TSK standard, polystyrene F-40, F-20, F-4, F-1, A-5000, A-2500, and A-1000 manufactured by Tosoh Corporation, and n- Make from 8 samples of propylbenzene.
  • the average particle diameter of the polymer particles (particularly self-dispersing polymer particles) in the present invention is preferably in the range of 10 to 400 nm in terms of volume average particle diameter, more preferably in the range of 10 to 200 nm, and still more preferably in the range of 10 to 100 nm. Particularly preferred is a range of 10 to 50 nm. Manufacturability is improved when the volume average particle diameter is 10 nm or more. Moreover, storage stability improves that a volume average particle diameter is 400 nm or less.
  • the particle size distribution of the polymer particles is not particularly limited, and may be either a wide particle size distribution or a monodispersed particle size distribution. Two or more kinds of the polymer particles having different particle size distributions may be mixed and used.
  • the average particle size and particle size distribution of the polymer particles are determined by measuring the volume average particle size by a dynamic light scattering method using a nanotrack particle size distribution measuring device UPA-EX150 (manufactured by Nikkiso Co., Ltd.). It is what
  • water-insoluble polymer forming the self-dispersing polymer particles include phenoxyethyl acrylate / methyl methacrylate / acrylic acid copolymer (50/45/5), phenoxyethyl acrylate / methyl methacrylate / acrylic acid copolymer.
  • the ink composition in the invention may contain one kind of the polymer particles (preferably self-dispersing polymer particles) or two or more kinds.
  • the content (solid content) of the polymer particles (preferably self-dispersing polymer particles) in the ink composition is preferably 0.5 to 5.0% by mass, based on the total amount of the ink composition, 0.5% More preferably, it is in the range of -3.0% by mass.
  • the ink composition in the present invention contains at least one polymerizable compound.
  • This polymerizable compound is a component that starts and cures when irradiated with active energy rays.
  • This polymerizable compound penetrates into the coating layer when coated paper is used as the recording medium, and is used together with the colorant particles or polymer particles to combine with the colorant particles or the polymer particles to agglomerate when in contact with the treatment liquid. Once captured, the image is enhanced by subsequent polymerization and curing.
  • the polymerizable compound in the present invention is preferably water-soluble.
  • water-soluble means that it can be dissolved in water at a certain concentration or higher, and may be any one that can be dissolved (desirably uniformly) in water-based ink or processing liquid.
  • the solubility may be increased by adding a water-soluble organic solvent to be described later, and it may be dissolved (desirably uniformly) in the ink.
  • the solubility in water is preferably 10% by mass or more, and more preferably 15% by mass or more.
  • a nonionic or cationic polymerizable compound is preferable in that it does not interfere with the reaction between the aggregating component, the pigment, and the polymer particles, and the solubility in water is 10% by mass or more (more preferably 15% by mass or more).
  • the polymerizable compound is preferable.
  • nonionic polymerizable monomers examples include polymerizable compounds such as (meth) acrylic monomers.
  • Examples of (meth) acrylic monomers include (meth) acrylic acid ester of polyhydric alcohol, (meth) acrylic acid ester of glycidyl ether of polyhydric alcohol, (meth) acrylic acid ester of polyethylene glycol, polyhydric alcohol
  • Examples include ultraviolet curable monomers and oligomers such as (meth) acrylic acid esters of ethylene oxide addition compounds and reaction products of polybasic acid anhydrides and hydroxyl group-containing (meth) acrylic acid esters.
  • the polyhydric alcohol may have a chain extended with an ethylene oxide chain by addition of ethylene oxide.
  • nonionic polymerizable compounds nonionic compounds 1 to 6
  • present invention is not limited to these.
  • an acrylate ester having two or more acryloyl groups in one molecule derived from a polyhydroxyl compound can also be used.
  • the polyhydroxyl compound include condensates of glycols, oligoethers, oligoesters, and the like.
  • nonionic polymerizable compounds include (meth) acrylic acid esters of polyols having two or more hydroxyl groups such as monosaccharides and disaccharides; and triethanolamine, diethanolamine, trishydroxyaminomethane, trishydroxyaminoethane, and the like.
  • the (meth) acrylic acid ester is also suitable.
  • nonionic polymerizable compound a water-soluble polymerizable compound having a (meth) acrylamide structure in the molecule is also suitable.
  • the polymerizable compound having a (meth) acrylamide structure in the molecule is more preferably a compound represented by the following general formula (1).
  • Q represents an n-valent group
  • R 1 represents a hydrogen atom or a methyl group
  • N represents an integer of 1 or more.
  • the compound represented by the general formula (1) is a compound in which an unsaturated vinyl monomer is bonded to the group Q by an amide bond.
  • R 1 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
  • the valence n of the group Q is 1 or more from the viewpoint of improving polymerization efficiency and ejection stability, preferably 1 or more and 6 or less, and more preferably 1 or more and 4 or less.
  • the polymerizable compound may contain a polyfunctional (meth) acrylamide compound with n ⁇ 2 in that the polymerization efficiency is excellent and, for example, the coating layer is prevented from being broken when coated paper is used. preferable.
  • the group Q includes a substituted or unsubstituted alkylene chain having 4 or less carbon atoms such as methylene, ethylene, propylene, butylene group, and further a pyridine ring, imidazole ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring. Examples thereof include a functional group having a saturated or unsaturated heterocyclic ring.
  • the group Q is preferably an alkyl group or a substituted alkyl group, and the alkyl has preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. Examples of the substituent when substituted include a hydroxyl group and an amino group.
  • the group Q represents a linking group.
  • the linking group is preferably a residue of a polyol compound containing an oxyalkylene group (preferably oxyethylene group), and a residue of a polyol compound containing 3 or more oxyalkylene groups (preferably oxyethylene group). Is particularly preferred.
  • the polyfunctional (meth) acrylamide compound has high polymerization ability and curing ability, for example, prevents the coating layer from being destroyed when coated paper is used, and has the effect of preventing the occurrence of stacker blocking and gloss unevenness.
  • the tetrafunctional (meth) acrylamide compound represented by following General formula (2) is preferable at the point played. This compound is a tetrafunctional (meth) acrylamide compound having four (meth) acrylamide structures as polymerizable groups in one molecule.
  • the (meth) acrylamide structure is also referred to as “(meth) acrylamide group”.
  • this compound exhibits curability based on a polymerization reaction due to application of energy such as active energy rays such as ⁇ rays, ⁇ rays, X rays, ultraviolet rays, visible rays, infrared rays, and electron beams, and heat.
  • energy such as active energy rays such as ⁇ rays, ⁇ rays, X rays, ultraviolet rays, visible rays, infrared rays, and electron beams, and heat.
  • the compound represented by the following general formula (2) exhibits water solubility and dissolves well in water-soluble organic solvents such as water and alcohol.
  • R 1 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
  • R ⁇ 1 > may mutually be same or different.
  • R 2 represents a linear or branched alkylene group having 2 to 4 carbon atoms.
  • a plurality of R 2 may be the same as or different from each other.
  • R 2 is preferably an alkylene group having 3 to 4 carbon atoms, more preferably an alkylene group having 3 carbon atoms, and particularly preferably a linear alkylene group having 3 carbon atoms.
  • the alkylene group for R 2 may further have a substituent, and examples of the substituent include an aryl group and an alkoxy group.
  • R 2 does not have a structure in which an oxygen atom and a nitrogen atom bonded to both ends of R 2 are bonded to the same carbon atom of R 2 .
  • R 2 is a linear or branched alkylene group that connects the oxygen atom and the nitrogen atom of the (meth) acrylamide group.
  • the alkylene group has a branched structure, the —O—C—N— structure (hemaminal structure) in which the oxygen atoms at both ends and the nitrogen atom of the (meth) acrylamide group are bonded to the same carbon atom in the alkylene group.
  • the compound represented by the general formula (2) does not include a compound having such a structure.
  • a compound having an —O—C—N— structure in the molecule is likely to decompose at the position of the carbon atom, so that it is easily decomposed during storage and causes a decrease in storage stability when contained in an ink composition. This is not preferable.
  • R 3 represents a divalent linking group, and a plurality of R 3 may be the same as or different from each other.
  • Examples of the divalent linking group represented by R 3 include an alkylene group, an arylene group, a heterocyclic group, or a group composed of a combination thereof, and an alkylene group is preferable.
  • the alkylene group may further include at least one group selected from —O—, —S—, and —NR a —.
  • R a represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 3 contains an alkylene group
  • examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, and a nonylene group.
  • the number of carbon atoms of the alkylene group represented by R 3 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1.
  • the alkylene group for R 3 may further contain at least one selected from —O—, —S—, and —NR a —.
  • alkylene group containing —O— examples include —C 2 H 4 —O—C 2 H 4 —, —C 3 H 6 —O—C 3 H 6 — and the like.
  • the alkylene group for R 3 may further have a substituent, and examples of the substituent include an aryl group and an alkoxy group.
  • R 3 contains an arylene group
  • examples of the arylene group include a phenylene group and a naphthylene group.
  • the carbon number of the arylene group of R 3 is preferably 6 to 14, and preferably 6 to 10. More preferably, 6 is particularly preferable.
  • the arylene group for R 3 may further have a substituent, and examples of the substituent include an alkyl group and an alkoxy group.
  • the heterocyclic group is preferably a 5-membered or 6-membered ring, which may be further condensed.
  • the heterocyclic ring may be an aromatic heterocyclic ring or a non-aromatic heterocyclic ring.
  • heterocyclic group examples include pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, And triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like.
  • an aromatic heterocyclic group is preferable, and pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole, and thiadiazole are preferable.
  • the heterocyclic group shown above is illustrated in a form in which the substitution position is omitted, the substitution position is not limited. For example, in the case of pyridine, substitution is made at the 2-position, 3-position, and 4-position. And can include all of these substitutions.
  • the heterocyclic group may further have a substituent, and examples of the substituent include an alkyl group, an aryl group, and an alkoxy group.
  • K in the general formula (2) represents 2 or 3.
  • C k H 2k may be a linear structure or a branched structure. However, k is the same within one C k H 2k O unit.
  • X, y and z each independently represents an integer of 0 to 6, preferably an integer of 0 to 5, and more preferably an integer of 0 to 3.
  • x + y + z satisfies 0 to 18, preferably satisfies 0 to 15, and more preferably satisfies 0 to 9.
  • a plurality of R 1 s each independently represent a hydrogen atom or a methyl group
  • a plurality of R 2 s each independently represent an alkylene group having 3 to 4 carbon atoms
  • a plurality of R 3 s each independently represent a carbon number 1 Represents an alkylene group having 6 to 6 (preferably 1 to 3 carbon atoms)
  • a plurality of k each independently represents 2 or 3
  • x, y, and z each independently represent an integer of 0 to 6; x + y + z Is preferably 0 to 15.
  • the compound represented by the general formula (2) can be produced, for example, according to the following scheme 1 or scheme 2.
  • the first step is a step of obtaining a polycyano compound by reaction of acrylonitrile and trishydroxymethylaminomethane.
  • the reaction in this step is preferably performed at 3 to 60 ° C. for 2 to 8 hours.
  • the second step is a step of reacting a polycyano compound with hydrogen in the presence of a catalyst to obtain a polyamine compound by a reduction reaction.
  • the reaction in this step is preferably performed at 20 to 60 ° C. for 5 to 16 hours.
  • the third step is a step of obtaining a polyfunctional acrylamide compound by an acylation reaction between a polyamine compound and acrylic acid chloride or methacrylic acid chloride.
  • the reaction in this step is preferably performed at 3 to 25 ° C. for 1 to 5 hours.
  • the acylating agent may be diacrylic anhydride or dimethacrylic anhydride instead of acid chloride.
  • the first step is a step of obtaining a nitrogen-protected aminoalcohol compound by introducing a protecting group with a benzyl group, benzyloxycarbonyl group or the like into the nitrogen atom of the aminoalcohol.
  • the reaction in this step is preferably performed at 3 to 25 ° C. for 3 to 5 hours.
  • the second step is a step of obtaining a sulfonyl compound by introducing a leaving group such as a methanesulfonyl group or p-toluenesulfonyl group into the OH group of the nitrogen-protected aminoalcohol compound.
  • the reaction in this step is preferably performed at 3 to 25 ° C. for 2 to 5 hours.
  • the third step is a step of obtaining an amino alcohol addition compound by SN2 reaction between a sulfonyl compound and trishydroxymethylnitromethane.
  • the reaction in this step is preferably performed at 3 to 70 ° C. for 5 to 10 hours.
  • the fourth step is a step of reacting an amino alcohol addition compound with hydrogen in the presence of a catalyst to obtain a polyamine compound by hydrogenation reaction.
  • the reaction in this step is preferably performed at 20 to 60 ° C. for 5 to 16 hours.
  • the fifth step is a step of obtaining a polyfunctional acrylamide compound by an acylation reaction between a polyamine compound and acrylic acid chloride or methacrylic acid chloride.
  • the reaction in this step is preferably performed at 3 to 25 ° C. for 1 to 5 hours.
  • the acylating agent may be diacrylic anhydride or dimethacrylic anhydride instead of acid chloride.
  • the compound obtained through the above steps can be obtained by purifying the reaction product solution by a conventional method.
  • it can be purified by liquid separation extraction using an organic solvent, crystallization using a poor solvent, column chromatography using silica gel, and the like.
  • the cationic polymerizable compound mentioned as an example of the polymerizable compound in the present invention is a compound having a cationic group and a polymerizable group such as an unsaturated double bond.
  • the cationic polymerizable compound for example, epoxy monomers and octacene monomers can be preferably used.
  • the cationic polymerizable compound is contained, the cationic property of the ink composition is increased due to the presence of the cationic group, and color mixing when an anionic ink is used is more effectively prevented.
  • Examples of the cationic polymerizable compound include N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl methacrylate, N, N-dimethylaminopropyl acrylate, N, N -Dimethylaminoacrylamide, N, N-dimethylaminomethacrylamide, N, N-dimethylaminoethylacrylamide, N, N-dimethylaminoethylmethacrylamide, N, N-dimethylaminopropylacrylamide, and N, N-dimethylaminopropyl Examples include methacrylamide and quaternized compounds thereof.
  • epoxy monomers examples include glycidyl ethers of polyhydric alcohols, glycidyl esters, and aliphatic cyclic epoxides. Furthermore, what has the following structure can be mentioned as an example of a cationic polymerizable compound.
  • R represents a polyol residue.
  • X represents H or CH 3
  • a ⁇ represents Cl ⁇ , HSO 3 — or CH 3 COO — .
  • Examples of the compound for introducing the polyol include glycerin, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, trimethylolpropane, trimethylolmethane, Examples thereof include trimethylolethane, pentaerythritol, bisphenol A, alicyclic bisphenol A, and condensates thereof.
  • Specific examples of the polymerizable compound having a cationic group are shown below.
  • the polymerizable compound in the present invention is preferably a polyfunctional monomer, preferably a bifunctional to hexafunctional monomer, from the viewpoint of enhancing the effect of preventing the occurrence of uneven glossiness and stacker blocking in addition to scratch resistance.
  • a bifunctional to tetrafunctional monomer is preferable from the viewpoint of achieving both good friction resistance and high scratch resistance.
  • the content ratio [q: p [mass ratio]] of the polymerizable compound (p) and the colorant (q) described in the present invention is preferably 1: 1 to 1:20, more preferably 2: 3. ⁇ 1: 15, more preferably 1: 2 to 1:10.
  • the content ratio (q: p) is 1: 1 or more, that is, the ratio of the polymerizable compound is not too small as compared with the colorant, the image adhesion is excellent.
  • the content ratio (q: p) is 1:20 or less, that is, within a range where the ratio of the polymerizable compound is not too much as compared with the colorant, it is advantageous in terms of dischargeability.
  • a polymeric compound can be contained individually by 1 type or in combination of 2 or more types.
  • the content of the polymerizable compound in the ink composition is preferably 15% by mass or more and less than 30% by mass, and more preferably 15% by mass or more and 25% by mass or less with respect to the total mass of the ink composition.
  • the content of the polymerizable compound is 15% by mass or more, the adhesion of the ink composition to the recording medium is improved, and the image strength is further increased, resulting in image scratch resistance, glossiness, and stacker blocking resistance. Excellent.
  • the content of the polymerizable compound is 30% by mass or less, it is advantageous in terms of the level difference (pile height) of the image.
  • the ink composition in the invention may contain at least one polymerization initiator that initiates polymerization of the polymerizable compound by active energy rays.
  • a polymerization initiator can be used individually by 1 type or in mixture of 2 or more types or using together with a sensitizer.
  • the polymerization initiator can contain a compound that can initiate a polymerization reaction of the polymerizable compound by active energy rays as appropriate.
  • the polymerization initiator include polymerization initiators (for example, photopolymerization initiators) that generate active species (radicals, acids, bases, etc.) by radiation or light, or electron beams.
  • photopolymerization initiator examples include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophene, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, p, p′-dichlorobenzophene, p, p'-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzyldimethyl ketal, tetramethylthiuram mono Sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, azobisisobutyronitrile, benzoin per
  • aromatic diazonium salts aromatic halonium salts, aromatic sulfonium salts, metallocene compounds such as triphenylsulfonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate and the like can be mentioned.
  • aromatic diazonium salts aromatic halonium salts, aromatic sulfonium salts, metallocene compounds such as triphenylsulfonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate and the like
  • 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one is preferred because it is highly compatible with ink and reduces gloss unevenness.
  • the content of the polymerization initiator in the ink composition is preferably 1 to 40% by mass with respect to the above-described polymerizable compound, and preferably 1 to 10%. The mass% is more preferable.
  • the content of the polymerization initiator is 1% by mass or more, the scratch resistance and scratch resistance of the image are further improved, which is advantageous for high-speed recording, and when it is 40% by mass or less, it is advantageous in terms of ejection stability. is there.
  • sensitizer examples include amines (aliphatic amines, amines containing aromatic groups, piperidine, etc.), ureas (allylic, o-tolylthiourea, etc.), sulfur compounds (sodium diethyldithiophosphate, aromatic sulfinic acid).
  • Soluble salts, etc. Soluble salts, etc.), nitrile compounds (N, N, di-substituted p-aminobenzonitrile, etc.), phosphorus compounds (tri-n-butylphosphine, netium diethyldithiophos feed, etc.), nitrogen compounds (Michler ketone, N-nitriso) Hydroxylamine derivatives, oxazolidine compounds, tetrahydro 1,3-oxazine compounds, formaldehyde, acetaldehyde and diamine condensates, etc.), chlorine compounds (carbon tetrachloride, hexachloroethane, etc.), polymerized amines of reaction products of epoxy resins and amines , Triethanolamine Acrylate, and the like.
  • a sensitizer can be contained in the range which does not impair the effect of this invention.
  • the ink composition in the present invention contains water, but the amount of water is not particularly limited. Among them, the preferable content of water is 10 to 99% by mass, more preferably 30 to 80% by mass, and still more preferably 50 to 70% by mass with respect to the total mass of the ink composition.
  • the ink composition in the present invention may contain a water-soluble organic solvent.
  • the content is preferably small, and is preferably less than 3% by mass with respect to the total mass of the ink composition.
  • the lower limit of the content of the water-soluble organic solvent is preferably 0.5% by mass with respect to the total mass of the ink composition in terms of improving the solubility of the polymerizable compound.
  • the effect of preventing the ink composition from drying, moistening or promoting penetration into paper can be obtained.
  • the water-soluble organic solvent include glycerin, 1,2,6-hexanetriol, trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, and dipropylene glycol.
  • Glycols 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 1,2-octanediol, 1,2-hexanediol, Polyhydric alcohols such as alkanediols such as 1,2-pentanediol and 4-methyl-1,2-pentanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Glycol ethers such as lenglycol monomethyl ether acetate, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; and saccharides, sugar alcohols, hyaluronic acids, carbon number described in paragraph [0116] of JP2011-42150A Examples thereof include 1 to 4 alkyl alcohols, other glycol ethers, 2-pyrrolidone, N-methyl-2-
  • water-soluble organic solvents can be used alone or in combination of two or more.
  • Polyhydric alcohols are also useful as drying inhibitors and wetting agents, and are preferred as penetrants. Specific examples thereof include aliphatic diols described in paragraph No. [0117] of JP2011-42150A.
  • examples of the water-soluble organic solvent include compounds represented by the following structural formula (1) (glycerin alkylene oxide adduct).
  • l + m + n 3 to 15.
  • l + m + n 3 to 12
  • AO represents an ethyleneoxy group (sometimes abbreviated as EO) and / or a propyleneoxy group (sometimes abbreviated as PO), and among them, a propyleneoxy group is preferable.
  • EO ethyleneoxy group
  • PO propyleneoxy group
  • alkylene oxide adduct of glycerin a commercially available product may be used.
  • alkylene oxide adduct of glycerin an ether of polypropylene glycol and glycerin
  • Sanix GP-250 average molecular weight 250
  • examples include GP-400 (average molecular weight 400), GP-600 (average molecular weight 600) [manufactured by Sanyo Chemical Industries, Ltd.], and paragraph [0126] of the same publication.
  • the ink composition in the present invention can contain at least one surfactant as required.
  • the surfactant can be used as a surface tension adjusting agent, for example.
  • As the surfactant a compound having a structure having both a hydrophilic part and a hydrophobic part in the molecule can be used effectively.
  • Anionic surfactants, cationic surfactants, amphoteric surfactants, nonions Either a surfactant or a betaine surfactant can be used.
  • the above water-soluble polymer may be used as a surfactant.
  • a nonionic surfactant is preferable, and an acetylene glycol derivative (acetylene glycol surfactant) is more preferable.
  • the acetylene glycol surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne-4, An alkylene oxide adduct of 7-diol can be mentioned, and at least one selected from these is preferable.
  • Examples of commercially available products of these compounds include E series such as Olphine E1010 manufactured by Nissin Chemical Industry Co., Ltd.
  • the surfactant When a surfactant (surface tension adjusting agent) is contained in the ink composition, the surfactant has a surface tension of 20 to 60 mN / m from the viewpoint of satisfactorily discharging the ink composition by an inkjet method. It is preferable to contain in the quantity of the range which can be adjusted to. From the viewpoint of surface tension, the surfactant is preferably contained in an amount that can be adjusted to 20 to 45 mN / m (preferably 25 to 40 mN / m).
  • the content of the surfactant in the ink composition is preferably 0.1% by mass or more based on the total amount of the ink composition, More preferably, the content is 0.1 to 10% by mass, and still more preferably 0.2 to 3% by mass.
  • the ink composition in the invention may contain other additives in addition to the above components.
  • Other additives include, for example, polymerization inhibitors, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension.
  • Well-known additives such as a regulator, an antifoamer, a viscosity regulator, a dispersion stabilizer, a rust inhibitor, a chelating agent, are mentioned.
  • the surface tension (25 ° C.) of the ink composition in the invention is not particularly limited, but is preferably 20 mN / m or more and 60 mN / m or less.
  • the surface tension is more preferably 20 mN / m or more and 45 mN / m or less, and further preferably 25 mN / m or more and 40 mN / m or less.
  • the surface tension of the ink composition is measured at 25 ° C. using an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).
  • the viscosity of the ink composition in the invention is not particularly limited, but is preferably 1.2 mPa ⁇ s or more and 15.0 mPa ⁇ s or less at 25 ° C., more preferably 2 mPa ⁇ s or more and less than 13 mPa ⁇ s. More preferably, it is 2.5 mPa ⁇ s or more and less than 10 mPa ⁇ s.
  • the viscosity of the ink composition is measured using a VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD) at 25 ° C.
  • the pH of the ink composition in the present invention is not particularly limited, but is preferably in the range of 7.5 to 10, more preferably in the range of 8 to 9, from the viewpoint of ink stability and aggregation rate.
  • the pH of the ink composition is 25 ° C., and is measured by a commonly used pH measuring device (for example, multi water quality meter MM-60R manufactured by Toa DKK Co., Ltd.).
  • the pH of the ink composition can be appropriately adjusted using an acidic compound or a basic compound.
  • an acidic compound and a basic compound the compound used normally can be especially used without a restriction
  • the drying process in the present invention is a process of drying the image formed in the ink application process.
  • the drying step at least a portion of water and at least a portion of the water-soluble organic solvent in the image (ink composition) formed on the recording medium by applying the ink composition in the ink applying step are removed by drying.
  • image formation is performed at a high speed, such as a method of forming an image by a single pass method in which ink is ejected in the main scanning direction to form one line in one scan, it is possible to ensure the sensitivity with which image formability is established. it can.
  • drying step of the present invention it is not always necessary to completely dry water or the water-soluble organic solvent.
  • Water or the water-soluble organic solvent is used in the image and the recording medium (particularly when the coated paper is used with coated paper ( It may remain in the pigment layer)).
  • the drying conditions in which 60 to 80% by mass of the water contained in the ink composition (image) applied in the maximum applied amount are removed are described below. It is preferable that at least a part of water and / or a water-soluble organic solvent contained in the ink composition applied on the recording medium in the ink application step is removed.
  • production of stacker blocking is suppressed as the quantity of the water and / or water-soluble organic solvent to be removed is 60 mass% or more. Further, when the amount of water to be removed is 80% by mass or less, the image adhesion is good.
  • the drying conditions may be set based on the maximum application amount of the ink composition in the ink application process that is appropriately set as necessary. By removing water in the ink composition containing the pigment under such dry conditions, the occurrence of stacker blocking is suppressed, and an image having excellent adhesion can be obtained.
  • the amount of drying in the drying step can be calculated as follows. That is, The amount of water W 0 contained in the image formed with the maximum amount of ink applied without providing the drying step, and the amount of water W 1 contained in the image formed with the maximum amount of ink applied with the drying step according to the predetermined drying conditions. And are measured respectively. Next, by obtaining the ratio of the difference between W 0 and W 1 to W 0 ((W 0 ⁇ W 1 ) / W 0 ⁇ 100 [mass%]), drying as the amount of water removed by the drying step is performed. The amount (mass%) is calculated. The amount of water contained in the image is measured by the Karl Fischer method. As the amount of water in the present invention, the amount of water measured under normal measuring conditions using a Karl Fischer moisture meter MKA-520 (manufactured by Kyoto Electronics Industry Co., Ltd.) is applied.
  • the amount of water (dry amount) in the ink composition that is removed in the drying step is the total amount of the ink composition that is applied with a maximum application amount of 15 ml / m 2 or less from the viewpoint that the curing efficiency after drying is kept good. 60 to 80% by mass is preferable, 65 to 80% by mass is more preferable, and 70 to 80% by mass is still more preferable with respect to the amount of water.
  • the drying is preferably started within 5 seconds from the time when the ink composition droplets land on the recording medium.
  • “within 5 seconds from the time of landing” means that the image is blown or heat is applied within 5 seconds from the landing of the ink droplet.
  • drying is started within 5 seconds after landing by transporting the recording medium into the drying area within 5 seconds after landing of the ink droplet.
  • the time from the ink droplet landing to the start of drying is more preferably within 3 seconds.
  • Drying can be performed by a heating means for heating with a heating element such as a nichrome wire heater, a blowing means using blowing air such as a dryer, or a combination of these.
  • a heating element such as a nichrome wire heater, a blowing means using blowing air such as a dryer, or a combination of these.
  • the heating method include a method of applying heat from a side opposite to the image forming surface of the recording medium with a heater, a method of applying warm air or hot air to the image forming surface of the recording medium, a heating method using an infrared heater, and the like. Can be mentioned. Heating may be performed by combining a plurality of these.
  • the curing step in the present invention is a step of curing the image by irradiating the image after dried in the above-described drying step with active energy rays.
  • active energy rays By irradiating active energy rays, the polymerizable compound in the ink composition is polymerized to form a cured film containing a pigment.
  • the active energy ray is not particularly limited as long as it can polymerize a polymerizable compound, and examples thereof include ⁇ rays, ⁇ rays, electron rays, X rays, ultraviolet rays, visible light, and infrared rays. Among these, ultraviolet rays are preferable from the viewpoint of versatility.
  • Examples of the source of active energy rays include an ultraviolet irradiation lamp (such as a halogen lamp and a high-pressure mercury lamp), a laser, an LED, and an electron beam irradiation device.
  • Irradiation can cure the entire image by placing a light source that irradiates active energy rays opposite the recording surface of the recording medium and irradiating the entire recording surface.
  • the curing step is provided at least after the ink application step, but is preferably provided after the ink application step and the treatment liquid application step.
  • the irradiation conditions of the active energy ray are not particularly limited as long as the polymerizable compound can be cured by causing a polymerization reaction.
  • the wavelength of the active energy ray is preferably in the range of 200 to 600 nm, more preferably in the range of 300 to 450 nm, and still more preferably in the range of 350 to 420 nm.
  • the output of the active energy ray is preferably at 5000 mJ / cm 2 or less, more preferably 10 ⁇ 4000mJ / cm 2, further preferably 20 ⁇ 3000mJ / cm 2.
  • the cooling step in the present invention is a step of cooling the image after being cured in the curing step with a temperature difference before and after cooling being 15 ° C. or more.
  • the image is once heated in the drying process, cured while maintaining a certain temperature after heating (for example, 60 ° C. to 70 ° C.), and then cooled in advance before the accumulation in the paper discharge accumulation unit.
  • the image is cooled such that the temperature difference before and after cooling (that is, the difference between the image temperature before cooling and the image temperature after cooling) is 15 ° C. or higher.
  • the image temperature before cooling refers to the temperature (° C.) of the image at the time when the irradiation of the image is completed in the curing step.
  • the image temperature after cooling refers to the temperature (° C.) of the image at the time when the recording medium is stacked (immediately after stacking) in the following stacking process.
  • the temperature difference between before and after cooling is preferably 20 ° C. or higher, and more preferably 25 ° C. or higher, for the same reason as described above.
  • the upper limit of the temperature difference before and after cooling is preferably 50 ° C. When the upper limit of the temperature difference is 50 ° C. or less, there is an advantage that excessive deformation of the image portion due to shrinkage can be suppressed.
  • the image temperature described above is a value measured by bringing a thermocouple into contact with the surface of the image to be measured.
  • the image temperature after cooling that is, the temperature of the image immediately after integration, is preferably 60 ° C. or less, more preferably 45 ° C. or less, from the viewpoint of preventing the occurrence of stacker blocking and gloss unevenness.
  • the range of 20 ° C. to 30 ° C. is more preferable from the viewpoint of preventing the occurrence.
  • the time from the end of image irradiation in the curing step to the start of cooling is preferably in the range of 0.5 to 5 seconds, and more preferably in the range of 0.5 to 3 seconds.
  • the image image cooling rate (cooling rate) during cooling is preferably in the range of 5 ° C./sec to 25 ° C./sec, more preferably in the range of 7.5 ° C./sec to 20 ° C./sec.
  • the environment for curing the image in the curing process is relatively 20 to 80 ° C. It is preferable that the humidity is 20% to 50%, and the cooling condition in the cooling step is 20 to 50 ° C. and the relative humidity is 20 to 50%.
  • the environment when the image is cured in the curing step is 20 ° C. More preferably, the relative humidity is 20% to 45% at -60 ° C, and the cooling conditions in the cooling step are 20% to 45% relative humidity at a temperature of 45 ° C or lower.
  • the cooling method in the cooling process is not particularly limited as long as it can actively lower the temperature of the image on the recording medium, and any method may be selected.
  • a method in which the recording medium is conveyed and passed through a cooling chamber (cooling zone) having an ambient temperature of, for example, 60 ° C. or less, for example, a method in which cold air of 60 ° C. or less is applied to the image surface on the recording medium Examples thereof include a method in which an image or a recording medium on which an image is recorded is brought into contact with a cooling body cooled to a temperature of 0 ° C. or lower.
  • the stacking step in the present invention is a step of stacking and stacking a plurality of recording media after cooling in the cooling step and collecting them in a paper discharge stacking unit. Once heated at the time of drying, cured, and then accumulated through cooling, stacker blocking and gloss unevenness occurring between the recording media due to accumulation are prevented.
  • Recording medium stacking refers to stacking sheet-like recording media on an arbitrary paper discharge stacking unit and collecting them in a bundle. Accumulate. In the present invention, for example, even when the number of stacked recording media reaches 1000 or more, the occurrence of stacker blocking is prevented. Even during the accumulation, it is preferable to cool by sending cooling air.
  • the cooling air is preferably arranged so as to flow from the cooling processing unit to the paper discharge stacking unit.
  • the image recording method of the present invention preferably has a treatment liquid application step.
  • the treatment liquid application step is a step of applying a treatment liquid containing an aggregating component that aggregates the components in the ink composition applied to the recording medium in the ink application step onto the recording medium.
  • the processing liquid applied on the recording medium and the ink composition applied on the recording medium in the ink application step come into contact with each other, and an image is formed by aggregating dispersed particles such as pigments in the ink composition. Is done.
  • the treatment liquid contains at least an aggregating component.
  • the aggregation component may be any of a compound capable of changing the pH of the ink composition, a polyvalent metal salt, and a cationic polymer.
  • a compound capable of changing the pH of the ink composition is preferable, and a compound capable of lowering the pH of the ink composition is more preferable.
  • Examples of compounds that can lower the pH of the ink composition include acids (acidic compounds).
  • Examples of the acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, Lactic acid, sulfonic acid, orthophosphoric acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, derivatives of these compounds, or salts thereof, etc.
  • An acid may be used individually by 1 type and may use 2 or more types together.
  • the pH (25 ° C.) of the treatment liquid is preferably 6 or less, more preferably 4 or less, still more preferably in the range of 1 to 4, and particularly preferably 1 to 3.
  • the pH (25 ° C.) of the ink composition is preferably 7.5 or more (more preferably 8.0 or more).
  • the pH (25 ° C.) of the ink composition is 8.0 or more, and the pH (25 ° C.) of the treatment liquid is 0.5 to 4. Some cases are preferred.
  • an acid having high water solubility is preferable, and an organic acid is preferable, an organic acid having 2 or more valences is more preferable, and an organic acid having 2 or more valences is more preferable.
  • the following organic acids are particularly preferred:
  • the organic acid having a valence of 2 or more is preferably an organic acid having a first pKa of 3.5 or less, more preferably 3.0 or less. Specific examples include phosphoric acid, oxalic acid, malonic acid, citric acid and the like.
  • the polyvalent metal salt and the cationic polymer that can be used as the aggregating component for example, the polyvalent metal salt and the cationic polymer described in paragraphs 0155 to 0156 of JP 2011-042150 A can be used. it can.
  • the aggregating components can be used alone or in combination of two or more.
  • the content of the aggregating component in the treatment liquid is preferably 1 to 50% by mass, more preferably 3 to 45% by mass, and still more preferably 5 to 40% by mass.
  • At least one of the treatment liquid and the ink composition of the present invention described above may contain at least one polymerization initiator.
  • the preferred range of the polymerization initiator is the same as that already described as the polymerization initiator usable in the ink composition, and the preferred embodiment is also the same.
  • the treatment liquid may further contain other additives as other components within the range not impairing the effects of the present invention.
  • additives include anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, UV absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, antifoaming agents
  • Known additives such as an agent, a viscosity modifier, a dispersant, a dispersion stabilizer, a rust inhibitor, and a chelating agent can be used.
  • the treatment liquid can be applied by applying a known method such as a coating method, an ink jet method, or an immersion method.
  • a coating method a known coating method using a bar coater, an extrusion die coater, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater or the like can be used.
  • the details of the inkjet method are as described above.
  • the treatment liquid application step may be provided either before or after the ink application step using the above-described ink composition.
  • an ink application process is provided after the treatment liquid application process is preferable.
  • the above-described ink application step is a step of providing the above-described ink composition on the treatment liquid provided on the recording medium in the main-treatment liquid application step provided after the main-treatment liquid application step. It is preferable.
  • the treatment liquid is applied in advance, and the ink composition is applied so as to come into contact with the processing liquid applied onto the recording medium.
  • a mode of imaging is preferred. Thereby, inkjet recording can be speeded up, and an image with high density and resolution can be obtained even at high speed recording.
  • the amount of the treatment liquid applied in the treatment liquid application step is not particularly limited as long as the ink composition can be aggregated, but preferably the amount of the aggregation agent applied is 0.1 g / m 2 or more. Can do. Among them, an amount that gives an amount of the flocculant of 0.2 to 0.7 g / m 2 is preferable. When the applied amount of the flocculant is 0.1 g / m 2 or more, good high-speed flocculence can be maintained according to various usage forms of the ink composition. Further, it is preferable that the amount of the flocculant applied is 0.7 g / m 2 or less because the surface properties of the applied recording medium are not adversely affected (such as a change in gloss).
  • an ink application step is provided after the treatment liquid application step, and the treatment liquid on the recording medium is heated and dried after the treatment liquid is applied on the recording medium and before the ink composition is applied. It is preferable to further provide a heat drying step. By heating and drying the treatment liquid in advance before the ink application step, ink colorability such as bleeding prevention is improved, and a visible image with good color density and hue can be recorded.
  • Heat drying can be performed by a known heating means such as a heater, a blowing means using blowing air such as a dryer, or a combination of these.
  • a heating method for example, a method of applying heat with a heater or the like from the side opposite to the treatment liquid application surface of the recording medium, a method of applying warm air or hot air to the treatment liquid application surface of the recording medium, or an infrared heater was used.
  • the heating method etc. are mentioned, You may heat combining these two or more.
  • FIG. 1 is an overall configuration diagram of an inkjet recording apparatus 10 according to an embodiment of the present invention.
  • the ink jet recording apparatus 10 of the present embodiment uses an ink composition (ultraviolet (UV) curable ink containing water as a main solvent; hereinafter also referred to as aqueous UV ink) on a sheet of paper (recording medium) P.
  • An ink jet recording apparatus that records an image by the ink jet method, and mainly performs a predetermined process on a paper feeding unit 12 that feeds the paper P and a surface (image recording surface) of the paper P fed from the paper feeding unit 12.
  • An image recording unit 18 that records an image by an ink jet method using aqueous UV ink on the surface of the sheet P, an ink drying processing unit 20 that performs a drying process on the sheet P on which an image is recorded by the image recording unit 18, and A UV irradiation processing unit 22 for fixing the image by performing UV irradiation processing (fixing processing) on P, and a paper discharge stacking unit 24 for discharging the paper P subjected to UV irradiation processing by the UV irradiation processing unit 22.
  • the sheet feeding unit 12 feeds the sheets P stacked on the sheet feeding table 30 to the processing liquid applying unit 14 one by one.
  • the sheet feeding unit 12 as an example of a sheet feeding unit mainly includes a sheet feeding table 30, a soccer device 32, a sheet feeding roller pair 34, a feeder board 36, a front pad 38, and a sheet feeding drum 40. .
  • the paper P is placed on the paper feed tray 30 in a bundled state in which a large number of sheets are stacked.
  • the sheet feed table 30 is provided so as to be lifted and lowered by a sheet feed table lifting device (not shown).
  • the drive of the paper feed platform lifting / lowering device is controlled in conjunction with the increase / decrease of the paper P loaded on the paper feed platform 30 so that the paper P positioned at the top of the bundle is always positioned at a constant height. Then, the paper feed table 30 is moved up and down.
  • the soccer device 32 picks up the sheets P stacked on the sheet feeding table 30 one by one from the top and feeds them to the pair of sheet feeding rollers 34.
  • the soccer device 32 includes a suction foot 32A that is movable up and down and swingable.
  • the suction foot 32A sucks and holds the upper surface of the paper P, and the paper P is fed from the paper feed table 30 to the paper feed roller pair 34.
  • Transport At this time, the suction foot 32A sucks and holds the top surface of the front end side of the paper P positioned at the top of the bundle, pulls up the paper P, and the pair of paper P that constitutes the paper feed roller pair 34 is pulled up. Insert between rollers 34A, 34B.
  • the paper feed roller pair 34 includes a pair of upper and lower rollers 34A and 34B that are pressed against each other.
  • One of the pair of upper and lower rollers 34A and 34B is a drive roller (roller 34A) and the other is a driven roller (roller 34B).
  • the drive roller (roller 34A) is driven by a motor (not shown) and rotates.
  • the motor is driven in conjunction with the feeding of the paper P.
  • the motor rotates the driving roller (roller 34A) in accordance with the timing.
  • the sheet P inserted between the pair of upper and lower rollers 34A, 34B is nipped by the rollers 34A, 34B and is sent out in the rotation direction of the rollers 34A, 34B (the installation direction of the feeder board 36).
  • the feeder board 36 is formed corresponding to the paper width, and receives the paper P sent out from the paper feed roller pair 34 and guides it to the front pad 38.
  • the feeder board 36 is installed so as to be inclined downward, and guides the paper P placed on the transport surface to the front pad 38 by sliding along the transport surface.
  • a plurality of tape feeders 36A for conveying the paper P are installed at intervals in the width direction.
  • the tape feeder 36A is formed in an endless shape, and is driven to rotate by a motor (not shown).
  • the paper P placed on the conveyance surface of the feeder board 36 is fed by the tape feeder 36A and conveyed on the feeder board 36.
  • a retainer 36B and a roller 36C are installed on the feeder board 36.
  • a plurality of retainers 36 ⁇ / b> B are arranged in a longitudinal line along the conveyance surface of the paper P (two in this example).
  • the retainer 36B is made of, for example, a leaf spring having a width corresponding to the sheet width, and is placed in pressure contact with the conveyance surface.
  • the paper P conveyed on the feeder board 36 by the tape feeder 36A passes through the retainer 36B, so that the unevenness is corrected.
  • the roller 36C is disposed between the front and rear retainers 36B.
  • the roller 36C is placed in pressure contact with the transport surface of the paper P.
  • the sheet P conveyed between the front and rear retainers 36B is conveyed while the upper surface is suppressed by the rollers 36C.
  • the front pad 38 corrects the posture of the paper P.
  • the front pad 38 is formed in a plate shape and is disposed orthogonal to the transport direction of the paper P. Further, it is driven by a motor (not shown) so as to be swingable.
  • the leading edge of the sheet P conveyed on the feeder board 36 is brought into contact with the front pad 38 to correct the posture (so-called skew prevention).
  • the front pad 38 swings in conjunction with the paper feeding to the paper feeding drum 40 and delivers the paper P whose posture has been corrected to the paper feeding drum 40.
  • the paper feed drum 40 receives the paper P fed from the feeder board 36 via the front pad 38 and conveys it to the processing liquid application unit 14.
  • the paper supply drum 40 is formed in a cylindrical shape and is driven to rotate by a motor (not shown).
  • a gripper 40A is provided on the outer peripheral surface of the paper feed drum 40, and the leading edge of the paper P is gripped by the gripper 40A.
  • the paper feed drum 40 conveys the paper P to the processing liquid application unit 14 while winding the paper P around the peripheral surface by gripping and rotating the leading edge of the paper P with the gripper 40A.
  • the processing liquid application unit 14 applies a predetermined processing liquid to the surface (image recording surface) of the paper P.
  • the treatment liquid application unit 14 mainly includes a treatment liquid application drum 42 that conveys the paper P, and a treatment liquid application unit 44 that applies a predetermined treatment liquid to the image recording surface of the paper P conveyed by the treatment liquid application drum 42.
  • the treatment liquid applied to the surface of the paper P is an aggregating agent having a function of aggregating the color material (pigment) in the aqueous UV ink that is ejected onto the paper P by the subsequent image recording unit 18.
  • the processing liquid application drum 42 receives the paper P from the paper supply drum 40 of the paper supply unit 12 and conveys the paper P to the processing liquid drying processing unit 16.
  • the treatment liquid application drum 42 is formed in a cylindrical shape and is driven to rotate by a motor (not shown).
  • a gripper 42A is provided on the outer peripheral surface of the treatment liquid applying drum 42, and the leading edge of the paper P is gripped by the gripper 42A.
  • the treatment liquid application drum 42 conveys the paper P to the treatment liquid drying processing unit 16 (one rotation) while the paper P is wound around the circumferential surface by gripping and rotating the leading edge of the paper P with the gripper 42A. To transport one sheet of paper P).
  • the rotation of the processing liquid application drum 42 and the paper supply drum 40 is controlled so that the timing of receiving and delivering the paper P matches each other. That is, it drives so that it may become the same peripheral speed, and it drives so that the position of a mutual gripper may match.
  • the treatment liquid application unit 44 applies the treatment liquid to the surface of the paper P conveyed by the treatment liquid application drum 42 by a roller.
  • the processing liquid application unit 44 mainly applies a coating roller 44A for applying the processing liquid to the paper P, a processing liquid tank 44B for storing the processing liquid, and a processing liquid stored in the processing liquid tank 44B. And a pumping roller 44C to be supplied to the roller 44A.
  • the processing liquid is applied with a roller, but the method of applying the processing liquid is not limited to this.
  • the structure which provides a process liquid using an inkjet head, and the structure which provides a process liquid by spraying can also be employ
  • the processing liquid drying processing unit 16 performs a drying process on the paper P having a processing liquid applied to the surface.
  • the processing liquid drying processing unit 16 mainly performs drying air (on the image recording surface of the paper P conveyed by the processing liquid drying processing drum 46, the processing liquid drying processing drum 46 that conveys the paper P, and the processing liquid drying processing drum 46.
  • the processing liquid drying processing drum 46 receives the paper P from the processing liquid application drum 42 of the processing liquid application unit 14 and conveys the paper P to the image recording unit 18.
  • the processing liquid drying processing drum 46 is formed of, for example, a frame assembled in a cylindrical shape, and is driven to rotate by a motor (not shown).
  • a gripper 46A is provided on the outer peripheral surface of the processing liquid drying processing drum 46, and the leading edge of the paper P is gripped by the gripper 46A.
  • the processing liquid drying processing drum 46 conveys the paper P to the image recording unit 18 by gripping and rotating the leading edge of the paper P with the gripper 46A.
  • processing liquid drying processing drum 46 of this example is provided with grippers 46A at two locations on the outer peripheral surface so that two sheets of paper P can be conveyed by one rotation.
  • the rotation of the processing liquid drying processing drum 46 and the processing liquid application drum 42 is controlled so that the timing of receiving and delivering the paper P is matched. That is, it drives so that it may become the same peripheral speed, and it drives so that the position of a mutual gripper may match.
  • the paper transport guide 48 is arranged along the transport path of the paper P by the processing liquid drying processing drum 46 and guides the transport of the paper P.
  • the processing liquid drying processing unit 50 is installed inside the processing liquid drying processing drum 46 and performs drying processing by blowing dry air toward the surface of the paper P conveyed by the processing liquid drying processing drum 46. Thereby, the solvent component in the treatment liquid is removed, and an ink aggregation layer is formed on the surface of the paper P.
  • the two processing liquid drying processing units 50 are arranged inside the processing liquid drying processing drum 46 and blow dry air toward the surface of the paper P conveyed by the processing liquid drying processing drum 46. .
  • the image recording unit 18 ejects droplets of aqueous ultraviolet curable color inks (water-based UV inks) of M, K, Y, and C colors on the image recording surface of the paper P to form the image recording surface of the paper P. Draw a color image.
  • the image recording unit 18 mainly presses the image recording drum 52 that conveys the paper P and the paper P that is conveyed by the image recording drum 52, so that the paper P is in close contact with the peripheral surface of the image recording drum 52.
  • An inline sensor that reads an image recorded on the paper P, and an inkjet head 56M, 56K, 56C, 56Y as an example of a discharge head that discharges ink droplets of M, K, Y, and C colors onto the paper P. 58, a mist filter 60 for capturing ink mist, and a drum cooling unit 62.
  • water-based UV ink is used as the ink ejected from each of the inkjet heads 56M, 56K, 56C, and 56Y.
  • the aqueous UV ink can be cured by irradiating with ultraviolet rays (UV) after droplet ejection.
  • the image recording drum 52 receives the paper P from the processing liquid drying processing drum 46 of the processing liquid drying processing unit 16 and conveys the paper P to the ink drying processing unit 20.
  • the image recording drum 52 is formed in a cylindrical shape and is driven to rotate by a motor (not shown).
  • a gripper 52A is provided on the outer peripheral surface of the image recording drum 52, and the leading edge of the paper P is gripped by the gripper 52A.
  • the image recording drum 52 conveys the paper P to the ink drying processing unit 20 while winding the paper P around the peripheral surface by gripping and rotating the leading edge of the paper P with the gripper 52A.
  • the image recording drum 52 has a plurality of suction holes (not shown) formed in a predetermined pattern on the peripheral surface thereof. The sheet P wound around the peripheral surface of the image recording drum 52 is conveyed while being sucked and held on the peripheral surface of the image recording drum 52 by being sucked from the suction holes. Thereby, the paper P can be conveyed with high smoothness.
  • suction from the suction hole acts only within a certain range, and acts between a predetermined suction start position and a predetermined suction end position.
  • the suction start position is set to the installation position of the sheet pressing roller 54
  • the suction end position is set to the downstream side of the installation position of the in-line sensor 58 (for example, set to a position for delivering the sheet to the ink drying processing unit 20). .) That is, at least at the installation position (image recording position) of the inkjet heads 56M, 56K, 56C, and 56Y and the installation position (image reading position) of the inline sensor 58, the paper P is attracted and held on the peripheral surface of the image recording drum 52.
  • the mechanism for attracting and holding the paper P on the peripheral surface of the image recording drum 52 is not limited to the above-described suction method using negative pressure, and a method using electrostatic suction can also be employed.
  • the image recording drum 52 of the present example is provided with grippers 52A at two locations on the outer peripheral surface so that two sheets of paper P can be conveyed by one rotation.
  • the rotation of the image recording drum 52 and the processing liquid drying processing drum 46 is controlled so that the timing of receiving and transferring the paper P to each other matches. That is, it drives so that it may become the same peripheral speed, and it drives so that the position of a mutual gripper may match.
  • the paper pressing roller 54 is disposed in the vicinity of the paper receiving position of the image recording drum 52 (the position where the paper P is received from the processing liquid drying processing drum 46).
  • the sheet pressing roller 54 is made of, for example, a rubber roller, and is installed in press contact with the peripheral surface of the image recording drum 52.
  • the paper P transferred from the processing liquid drying processing drum 46 to the image recording drum 52 is nipped by passing through the paper pressing roller 54 and is brought into close contact with the peripheral surface of the image recording drum 52.
  • the four inkjet heads 56M, 56K, 56C, and 56Y are arranged at a constant interval along the transport path of the paper P by the image recording drum 52.
  • Each of the inkjet heads 56M, 56K, 56C, and 56Y includes, for example, a line head corresponding to the paper width, and is arranged so that the nozzle surface faces the peripheral surface of the image recording drum 52.
  • Each of these inkjet heads 56M, 56K, 56C, and 56Y is conveyed by the image recording drum 52 by ejecting droplets of aqueous UV ink from the nozzle row formed on the nozzle surface toward the image recording drum 52. An image is recorded on the paper P.
  • the plurality of inkjet heads 56M, 56K, 56C, and 56Y are preferably set to eject the aqueous UV ink so that the total amount of the aqueous UV ink on the paper P is 15 ml / m 2 or less at the maximum. This is because in the apparatus configuration of the present embodiment, the curability of the aqueous UV ink by the UV irradiation processing unit 22 can be ensured.
  • the inline sensor 58 is installed on the downstream side of the rearmost ink jet head 56K with respect to the conveyance direction (arrow D direction) of the paper P by the image recording drum 52, and is recorded by the ink jet heads 56M, 56K, 56C, and 56Y. Read the image.
  • the in-line sensor 58 is composed of, for example, a line scanner, and reads images recorded by the inkjet heads 56M, 56K, 56C, and 56Y from the paper P conveyed by the image recording drum 52.
  • a contact prevention plate 59 is installed in the vicinity of the inline sensor 58 on the downstream side of the inline sensor 58.
  • the contact prevention plate 59 prevents the paper P from coming into contact with the in-line sensor 58 when the paper P is lifted due to a conveyance failure or the like.
  • the mist filter 60 is disposed between the rearmost inkjet head 56Y and the inline sensor 58, and sucks air around the image recording drum 52 to capture the ink mist. In this way, by sucking the air around the image recording drum 52 and capturing the ink mist, the ink mist can be prevented from entering the in-line sensor 58 and reading errors can be prevented.
  • the drum cooling unit 62 cools the image recording drum 52 by blowing cold air onto the image recording drum 52.
  • the drum cooling unit 62 mainly includes an air conditioner (not shown) and a duct 62 ⁇ / b> A that blows cool air supplied from the air conditioner onto the peripheral surface of the image recording drum 52.
  • the duct 62 ⁇ / b> A cools the image recording drum 52 by blowing cool air to an area other than the conveyance area of the paper P against the image recording drum 52.
  • the duct 62A blows cold air to the area of the lower half of the image recording drum 52 to record the image.
  • the drum 52 is cooled.
  • the air outlet of the duct 62 ⁇ / b> A is formed in an arc shape so as to cover substantially the lower half of the image recording drum 52, and cold air is blown onto the region of the substantially lower half of the image recording drum 52.
  • the temperature at which the image recording drum 52 is cooled is determined by the relationship with the temperature of the inkjet heads 56M, 56K, 56C, and 56Y (particularly the temperature of the nozzle surface), and is higher than the temperature of the inkjet heads 56M, 56K, 56C, and 56Y. It is cooled to a low temperature. Thereby, it is possible to prevent dew condensation on the inkjet heads 56M, 56K, 56C, and 56Y. That is, by making the temperature of the image recording drum 52 lower than that of the inkjet heads 56M, 56K, 56C, and 56Y, condensation can be induced on the image recording drum side, and condensation occurring on the inkjet heads 56M, 56K, 56C, and 56Y. (Especially, condensation on the nozzle surface) can be prevented.
  • the ink drying processing unit 20 performs a drying process on the paper P after image recording, and removes liquid components remaining on the recording surface of the paper P.
  • the ink drying processing unit 20 mainly includes a chain gripper 64 that transports the paper P on which an image is recorded, and back tension application as an example of a back tension application unit that applies back tension to the paper P transported by the chain gripper 64.
  • a mechanism 66 and an ink drying processing unit 68 as an example of a drying unit for drying the paper P conveyed by the chain gripper 64 are included.
  • the chain gripper 64 is a paper transport mechanism commonly used in the ink drying processing unit 20, the UV irradiation processing unit 22, and the paper discharge stacking unit 24.
  • the chain gripper 64 receives the paper P delivered from the image recording unit 18, The paper is conveyed to the paper discharge stacking unit 24.
  • the chain gripper 64 mainly includes a first sprocket 64A installed in the vicinity of the image recording drum 52, a second sprocket 64B installed in the paper discharge stacking unit 24, a first sprocket 64A, and a second sprocket 64B.
  • An endless chain 64C wound around the chain a plurality of chain guides (not shown) for guiding the running of the chain 64C, and a plurality of grippers 64D attached to the chain 64C at a constant interval.
  • the first sprocket 64A, the second sprocket 64B, the chain 64C, and the chain guide are each paired and disposed on both sides of the paper P in the width direction.
  • the gripper 64D is installed over a chain 64C provided as a pair.
  • the first sprocket 64A is installed close to the image recording drum 52 so that the paper P delivered from the image recording drum 52 can be received by the gripper 64D.
  • the first sprocket 64A is rotatably supported by a bearing (not shown) and is connected to a motor (not shown).
  • the chain 64C wound around the first sprocket 64A and the second sprocket 64B travels by driving this motor.
  • the second sprocket 64B is installed in the paper discharge stacking unit 24 so that the paper P received from the image recording drum 52 can be collected by the paper discharge stacking unit 24. That is, the installation position of the second sprocket 64B is the end of the transport path of the paper P by the chain gripper 64.
  • the second sprocket 64B is pivotally supported by a bearing (not shown) and is rotatably provided.
  • the chain 64C is formed in an endless shape and is wound around the first sprocket 64A and the second sprocket 64B.
  • the chain guide is arranged at a predetermined position and guides the chain 64C to travel along a predetermined path (that is, guides the paper P to travel along a predetermined transport path).
  • the second sprocket 64B is disposed at a position higher than the first sprocket 64A. For this reason, a travel route in which the chain 64C is inclined in the middle is formed.
  • the travel path includes a first horizontal transport path 70A, an inclined transport path 70B, and a second horizontal transport path 70C.
  • the first horizontal conveyance path 70A is set to the same height as the first sprocket 64A, and the chain 64C wound around the first sprocket 64A is set to run horizontally.
  • the second horizontal conveyance path 70C is set to the same height as the second sprocket 64B, and the chain 64C wound around the second sprocket 64B is set to travel horizontally.
  • the inclined conveyance path 70B is set between the first horizontal conveyance path 70A and the second horizontal conveyance path 70C, and is set so as to connect the first horizontal conveyance path 70A and the second horizontal conveyance path 70C.
  • the chain guide is disposed so as to form the first horizontal conveyance path 70A, the inclined conveyance path 70B, and the second horizontal conveyance path 70C. Specifically, the chain guide is disposed at least at a junction point between the first horizontal conveyance path 70A and the inclined conveyance path 70B and at a junction point between the inclined conveyance path 70B and the second horizontal conveyance path 70C.
  • a plurality of grippers 64D are attached to the chain 64C at regular intervals.
  • the attachment interval of the gripper 64D is set in accordance with the reception interval of the paper P from the image recording drum 52. That is, it is set according to the reception interval of the paper P from the image recording drum 52 so that the paper P sequentially delivered from the image recording drum 52 can be received from the image recording drum 52 at the same timing.
  • the chain gripper 64 has the above configuration. As described above, when a motor (not shown) connected to the first sprocket 64A is driven, the chain 64C travels. The chain 64C travels at the same speed as the peripheral speed of the image recording drum 52. The timing is adjusted so that the paper P delivered from the image recording drum 52 can be received by each gripper 64D.
  • the back tension applying mechanism 66 applies a back tension to the paper P that is conveyed while its tip is gripped by the chain gripper 64.
  • the back tension applying mechanism 66 mainly includes a guide plate 72 and a plurality of suction fans that suck air from a plurality of suction holes formed on the upper surface of the guide plate 72.
  • the lower surface of the guide plate 72 is provided with a number of holes for discharging the sucked air.
  • the guide plate 72 is, for example, a hollow box plate having a width corresponding to the paper width.
  • the guide plate 72 is disposed along the transport path of the paper P by the chain gripper 64 (that is, the travel path of the chain).
  • the guide plate 72 is disposed along the chain 64C that travels along the first horizontal transport path 70A and the inclined transport path 70B, and is disposed at a predetermined distance from the chain 64C.
  • the sheet P conveyed by the chain gripper 64 has its back surface (the surface on which no image is recorded) sliding on the upper surface of the guide plate 72 (the surface facing the chain 64C: the sliding contact surface). Be transported.
  • a large number of suction holes are formed in a predetermined pattern on the sliding surface (upper surface) of the guide plate 72.
  • the guide plate 72 is formed of a hollow box plate. The suction fan sucks the hollow portion (inside) of the guide plate 72. As a result, air is sucked from the suction holes formed in the sliding contact surface.
  • the guide plate 72 since the guide plate 72 is disposed along the chain 64C that travels along the first horizontal conveyance path 70A and the inclined conveyance path 70B, the guide plate 72 conveys the first horizontal conveyance path 70A and the inclined conveyance path 70B. While it is being applied, back tension is applied.
  • the ink drying processing unit 68 is installed inside the chain gripper 64 (particularly the first half side and the second half side of the portion constituting the first horizontal transport path 70A), and is for the paper P transported through the first horizontal transport path 70A. Apply drying treatment.
  • the ink drying processing unit 68 blows dry air on the recording surface of the paper P transported through the first horizontal transport path 70A, so that the amount of water on the paper P including water in the aqueous UV ink is changed to UV irradiation processing. It is preferable to dry the paper P so that it becomes 3.0 g / m 2 or less before the irradiation of the ultraviolet rays by the unit 22.
  • a plurality of ink drying processing units 68 are arranged along the first horizontal conveyance path 70A. This number of installations is set according to the processing capacity of the ink drying processing unit 68, the conveyance speed (that is, the printing speed) of the paper P, and the like. That is, the sheet P received from the image recording unit 18 is set so that it can be dried while being conveyed through the first horizontal conveyance path 70A. Therefore, the length of the first horizontal conveyance path 70A is also set in consideration of the capability of the ink drying processing unit 68.
  • the UV irradiation processing unit 22 irradiates the image recorded using the aqueous UV ink with ultraviolet rays (UV) to fix the image.
  • the UV irradiation processing unit 22 mainly includes a chain gripper 64 that transports the paper P, a back tension applying mechanism 66 that applies back tension to the paper P transported by the chain gripper 64, and a paper transported by the chain gripper 64.
  • a UV irradiation unit 74 as an example of a fixing unit that irradiates P with ultraviolet rays.
  • the chain gripper 64 and the back tension applying mechanism 66 are used together with the ink drying processing unit 20 and the paper discharge stacking unit 24.
  • the UV irradiation unit 74 is installed inside the chain gripper 64 (in particular, inside the portion constituting the inclined conveyance path 70B), and irradiates the recording surface of the paper P conveyed through the inclined conveyance path 70B with ultraviolet rays.
  • the UV irradiation unit 74 includes an ultraviolet lamp (UV lamp), and a plurality of UV irradiation units 74 are arranged along the inclined conveyance path 70B. Then, ultraviolet rays are irradiated toward the recording surface of the paper P that is conveyed along the inclined conveyance path 70B.
  • the number of installed UV irradiation units 74 is set according to the conveyance speed (ie, printing speed) of the paper P.
  • the length of the inclined conveyance path 70B is also set in consideration of the conveyance speed of the paper P and the like.
  • a cooling processing unit 80 is provided in the second horizontal conveyance path 70C. 2 and 3 show details of the cooling processing unit 80.
  • the cooling processing unit 80 includes a plurality of fans 82 that are an example of a cooling device that blows air (air) onto a sheet at an upper position facing the sheet conveyed by the conveyance belt, And a cooler 84 as an example of a cooling device that lowers the ambient temperature of the paper.
  • the plurality of fans 82 are arranged along the direction orthogonal to the moving direction of the chain 64C (the direction intersecting the sheet conveying direction) and conveyed by the chain 64C. It is arranged to blow air toward the upstream side of the sheet conveyance direction. That is, the plurality of fans 82 blows air over the entire recording surface of the sheet from the downstream side in the conveyance direction of the sheet conveyed by the chain 64C to the upstream side in the conveyance direction.
  • four fans 82 are provided, but the number of fans 82 can be changed as appropriate.
  • the plurality of fans 82 blows air from the downstream side in the conveyance direction to the upstream side in the conveyance direction.
  • the plurality of fans 82 blows air from the downstream side in the conveyance direction to the upstream side in the conveyance direction.
  • By spraying paper fluttering can be suppressed.
  • by blowing air from the downstream side of the paper conveyance direction toward the upstream side of the conveyance direction heat from the ink drying processing unit 20 and the UV irradiation processing unit 22 is transmitted to the paper conveyed through the cooling processing unit 80. Is to be suppressed.
  • the paper conveyance direction and the direction of the wind from the fan 82 are opposite, and the time that the wind is hitting the paper becomes longer due to the relationship between the paper and the relative speed of the wind.
  • the cooler 84 is disposed slightly downstream of the fan 82 in the paper transport direction and above the chain 64C that moves around.
  • the cooler 84 includes an air outlet 84B formed in the lower portion of the housing 84A, and a heat exchanger 84C disposed inside the housing 84A.
  • the heat exchanger 84C cools the gas introduced into the housing 84A from the outside by a fan (not shown), and the gas cooled by the heat exchanger 84C is blown out from the outlet 84B by the fan.
  • the cooling air blown from the outlet 84B passes through the gap between the upper side chain 64C made of a chain member and is sent to the lower side chain 64C (paper to be conveyed).
  • a plurality of fans 82 are provided at positions where the cooling air blown from the air outlet 84 ⁇ / b> B of the cooler 84 hits, and the cooling air is blown onto the paper by the plurality of fans 82. Moreover, you may set so that the ventilation direction of a cooling wind may turn into the direction of the several fan 82 by adjusting the direction of the louver provided in the blower outlet 84B.
  • the cooler 84 since the cooler 84 is disposed above the sheet conveyed through the chain 64C, and the cool air from the cooler 84 comes down, the sheet is efficiently cooled.
  • the cooler 84 has a temperature (for example, 15 ° C. to 45 ° C.) lower than the temperature at the time of curing (for example, 60 to 80 ° C.) in the UV curing processing unit. To cool).
  • the heat exchanger 84C circulates refrigerant and cools the gas by condensation / evaporation.
  • the heat exchanger 84C is not limited to this, and uses a device or a pelcher element that sends cold air using a heat exchanger cooled by a water flow. Various configurations such as those can be used.
  • the cooling air is sent by the cooler 84, and the air is blown onto the paper by a plurality of fans 82 provided at positions where the cooling air hits, whereby the cured paper is an image at the time of curing. It is cooled to a temperature range that is 15 ° C. or more lower than the temperature.
  • the plurality of fans 82 are not provided with a function of cooling the air blown onto the paper, but a configuration in which a heat exchanger is provided inside the plurality of fans 82 and the cooling air is blown onto the paper. It is good.
  • the cooler 84 can be omitted.
  • the paper discharge stacking unit 24 collects the paper P on which a series of image recording processing has been performed.
  • the paper discharge stacking unit 24 mainly includes a chain gripper 64 that transports the UV irradiated paper P and a paper discharge tray 76 that stacks and collects the paper P.
  • the chain gripper 64 is used in common with the ink drying processing unit 20 and the UV irradiation processing unit 22.
  • the chain gripper 64 releases the paper P on the paper discharge tray 76 and stacks the paper P on the paper discharge tray 76.
  • it is preferable to cool the image by sending cooling air also in the paper discharge stacking unit.
  • the cooling air is preferably arranged so as to flow from the cooling processing unit to the paper discharge stacking unit.
  • the paper discharge tray 76 stacks and collects the paper P released from the chain gripper 64.
  • the paper discharge tray 76 is provided with a paper pad (a front paper pad, a rear paper pad, a horizontal paper pad, etc.) so that the sheets P are stacked in an orderly manner (not shown).
  • the paper discharge tray 76 is provided so as to be lifted and lowered by a paper discharge tray lifting / lowering device (not shown).
  • the discharge platform lifting device is controlled in conjunction with the increase / decrease of the paper P stacked on the paper discharge tray 76 so that the uppermost paper P is always positioned at a certain height.
  • the paper table 76 is moved up and down.
  • Example 1 ⁇ Preparation of cyan ink> (Preparation of Cyan Dispersion C1)
  • a reaction vessel 6 parts of styrene, 11 parts of stearyl methacrylate, 4 parts of styrene macromer AS-6 (manufactured by Toa Gosei Co., Ltd.), 5 parts of Plenmer PP-500 (manufactured by NOF Corporation), 5 parts of methacrylic acid, 2 parts -0.05 part of mercaptoethanol and 24 parts of methyl ethyl ketone were added to prepare a mixed solution.
  • styrene 14 parts of styrene, 24 parts of stearyl methacrylate, 9 parts of styrene macromer AS-6 (manufactured by Toagosei Co., Ltd.), 9 parts of Plenmer PP-500 (manufactured by NOF Corporation), 10 parts of methacrylic acid 2-mercaptoethanol (0.13 parts), methyl ethyl ketone (56 parts), and 2,2′-azobis (2,4-dimethylvaleronitrile) (1.2 parts) were added to prepare a mixed solution.
  • the mixed solution in the reaction vessel was heated to 75 ° C. while stirring, and the mixed solution in the dropping funnel was gradually dropped over 1 hour.
  • a solution prepared by dissolving 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) in 12 parts of methyl ethyl ketone was added dropwise over 3 hours. Aged at 80 ° C. for 2 hours to obtain a polymer dispersant solution.
  • a part of the obtained polymer dispersant solution was isolated by removing the solvent, and the obtained solid content was diluted to 0.1% by mass with tetrahydrofuran to obtain a high-speed GPC (gel permeation chromatography) HLC- Three TSKgeL SuperHZM-H, TSKgeL SuperHZ4000, and TSKgeL SuperHZ2000 (manufactured by Tosoh Corporation) were connected in series at 8220 GPC, and the weight average molecular weight was measured. As a result, the weight average molecular weight was 25,000 in terms of polystyrene.
  • the acid value was 80 mgKOH / g.
  • Pigment Blue 15: 3 (produced by Dainichi Seika Co., Ltd.) as a cyan pigment
  • 40.0 g of methyl ethyl ketone, 1 mol / L (liter;
  • 8.0 g of sodium hydroxide and 82.0 g of ion-exchanged water were supplied to the vessel together with 300 g of 0.1 mm zirconia beads, and dispersed at 1000 rpm for 6 hours with a ready mill disperser (manufactured by Imex).
  • the obtained dispersion was concentrated under reduced pressure using an evaporator until the methyl ethyl ketone was sufficiently distilled off, and further concentrated until the concentration of the water-dispersible pigment reached 10% by mass to obtain a cyan dispersion C1 in which the water-dispersible pigment was dispersed.
  • the volume average particle diameter (secondary particles) of the obtained cyan dispersion liquid C1 was measured by a dynamic light scattering method using a Microtorac particle size distribution analyzer (Version 10.1.2-211BH (trade name), manufactured by Nikkiso Co., Ltd.). Was 77 nm.
  • component A a component derived from benzyl methacrylate, a component derived from methyl methacrylate, and a component derived from methacrylic acid
  • component B a component derived from benzyl methacrylate
  • component C a component derived from methacrylic acid
  • the glass transition temperature (Tg) of the self-dispersing polymer particles P-1 was measured by the following method and found to be 85 ° C. ⁇ Measurement of Tg> An aqueous dispersion of self-dispersing polymer particles having a solid content of 0.5 g was dried under reduced pressure at 50 ° C. for 4 hours to obtain a polymer solid content. Using the obtained polymer solid content, Tg was measured with a differential scanning calorimeter (DSC) EXSTAR 6220 manufactured by SII Nanotechnology. The measurement condition was that a sample amount of 5 mg was sealed in an aluminum pan, and the DSC peak top value of the measurement data at the second temperature increase was defined as Tg under the following temperature profile in a nitrogen atmosphere.
  • DSC differential scanning calorimeter
  • the processing liquid was prepared by mixing components having the following composition.
  • Ibest white paperboard (coated paper), manufactured by Nippon Daishowa Paperboard Co., Ltd.) was prepared as a recording medium.
  • an ink jet recording apparatus 10 having the same structure as that shown in FIGS. 1 to 3 was prepared.
  • the ink jet recording apparatus 10 accommodates a recording medium P that is a recording sheet and feeds the recording medium P to a conveyance path, and the surface (image recording surface) of the recording medium P fed from the paper feeding unit 12.
  • An image forming unit 18 that applies cyan ink by an ink jet method and records an image
  • an ink drying processing unit 20 that performs a drying process of the recording medium P on which the image is recorded
  • an ultraviolet ray ( UV irradiation processing unit 22 for fixing an image by performing (UV) irradiation (fixing processing)
  • a paper discharge stacking unit 24 for discharging and stacking the recording medium P after UV irradiation.
  • the recording medium is accommodated in the paper feeding unit 12 of the ink jet recording apparatus, and further, the processing liquid tank 44B included in the processing liquid applying unit of the processing liquid applying unit and the ink storage tank (not shown) communicating with the ink jet head 56C are respectively described above. And a cyan ink were loaded.
  • the inkjet head is a 1200 dpi (dot per inch) / 10 inch wide full line head (driving frequency: 25 kHz, recording medium conveyance speed 530 mm / sec), and can record by discharging each color in the main scanning direction in a single pass. It has become.
  • a solid image was recorded in order to evaluate stacker blocking and gloss unevenness, and the solid image was formed by discharging ink over the entire paper surface of the recording medium cut to A5 size.
  • cyan ink was ejected at a resolution of 1200 dpi ⁇ 600 dpi and an ink droplet amount of 3.5 pl, and the amount of treatment liquid applied to the recording medium was 5 ml / m 2 .
  • a processing liquid was applied onto the recording medium by the processing liquid application unit 14, and then the processing liquid was dried by the processing liquid drying processing unit 16.
  • the processing liquid drying zone was allowed to pass by 1000 msec from the start of discharge of the processing liquid.
  • the applied treatment liquid was adjusted to a predetermined dry amount by changing the air volume by blowing hot air at 50 ° C. and 3 m / sec with a blower on the application surface.
  • the image recording unit 18 an image was recorded by ejecting cyan ink in a single pass by the inkjet head 56C. Thereafter, the ink drying processing unit 20 blows warm air at 50 ° C.
  • the recording medium P was dried so as to be 1.0 g / m 2 or less.
  • the UV irradiation processing unit 22 applied UV irradiation to the image recorded using cyan ink under environmental conditions of a temperature of 60 ° C. and a relative humidity of 45% to fix (cure) the image.
  • the temperature of the image part at this time was 80 degreeC.
  • the temperature of the image part was measured by attaching a thermocouple to the image surface.
  • the recording medium P on which the image is recorded is transported to the cooling processing unit, and the temperature of the image unit is set to 10 ° C./sec by supplying air at 20 ° C. and 3 m / sec to the image recording surface by a blower. It cooled to 60 degreeC with the temperature-fall rate. Cooling was started by supplying air when UV irradiation was finished (image curing was finished) and 0.5 seconds had passed. After cooling, the recording medium P was unloaded and collected in the paper discharge stacking unit 24, and the recording medium P was collected. At this time, cooling air is blown to the paper discharge stacking unit 24. The temperature of the image portion of the recovered recording medium P was measured by attaching a thermocouple to the image surface at the time of recovery, and was 55 ° C.
  • Stacker blocking As described above, the eye vests on which the solid images were recorded were continuously discharged to the paper discharge stacking unit and stacked 1000 sheets. After the stacking, the eye vests were left for 24 hours at 60 ° C. and 30% RH. After leaving, the tenth recording medium from the bottom was taken out and evaluated according to the following evaluation criteria. In addition, stacker blocking is a range in which A to C are acceptable in practical use.
  • C Image defects due to peeling of about 1 to 2 mm are observed in part of the image.
  • D Image defects due to peeling of about 1 to 2 mm are observed over the entire image.
  • E Image destruction is observed due to adhesion of the image over the entire surface and peeling of a large area.
  • Example 2 In Example 1, except that the polymerizable compound in the cyan ink, the monomer composition and Tg of the self-dispersing polymer particles, the aggregation component of the treatment liquid, and the cooling conditions during cooling were changed as shown in Table 1 below. In the same manner as in Example 1, images were recorded, and stacker blocking and gloss unevenness were evaluated. The evaluation results are shown in Table 1 below. In Examples 16 to 19, polyethyleneimine (cationic polymer) was used in place of malonic acid as the aggregation component of the treatment liquid.
  • Example 1 In Example 1, the same manner as in Example 1 except that the polymerizable compound in the cyan ink, the monomer composition and Tg of the self-dispersing polymer particles, and the cooling conditions during cooling were changed as shown in Table 1 below. Images were recorded, and stacker blocking and gloss unevenness were evaluated. The evaluation results are shown in Table 1 below.
  • the self-dispersing polymer particles used in Examples 2 to 31 and Comparative Examples 1 to 13 were synthesized except that the types and ratios of the monomers used in the synthesis of the self-dispersing polymer particles P-1 were changed.
  • the same method as the synthesis of the conductive polymer particle P-1 was performed.
  • the detail of the synthesis method of the tetrafunctional (meth) acrylamide 1 and the tetrafunctional (meth) acrylamide 2 of Table 1 is as follows.

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  • Materials Engineering (AREA)
  • Toxicology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

Procédé de formation d'image, comprenant une étape de transfert d'encre destinée à transférer sur un support d'enregistrement une composition d'encre comprenant un colorant, de l'eau, un composé polymérisable et des particules de polymère ayant une température de transition vitreuse de 80 à 150 °C, et à enregistrer une image, une étape de séchage destinée à sécher l'image, une étape de durcissement destinée à faire durcir l'image par exposition de l'image séchée à des rayons d'énergie active, une étape de refroidissement destinée à refroidir l'image durcie de sorte que la différence de température avant et après refroidissement soit d'au moins 15 °C, et une étape d'accumulation destinée à empiler une pluralité de feuilles du support d'enregistrement refroidi.
PCT/JP2013/074545 2012-09-24 2013-09-11 Procédé d'enregistrement d'image WO2014045969A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017218523A (ja) * 2016-06-08 2017-12-14 株式会社リコー インク及びインクカートリッジ
EP3909782A1 (fr) * 2020-05-14 2021-11-17 Ricoh Company, Ltd. Dispositif et procédé de formation d'images

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005307198A (ja) * 2004-03-26 2005-11-04 Canon Inc 活性エネルギー線硬化型水性インク、それを用いたインクジェット記録方法、インクカートリッジ、記録ユニット及びインクジェット記録装置
JP2007277380A (ja) * 2006-04-05 2007-10-25 Canon Inc 水性活性エネルギー線硬化型インク、インクジェット記録方法及び記録物
JP2009256607A (ja) * 2008-03-17 2009-11-05 Nitto Denko Corp アクリル系粘着剤、アクリル系粘着剤層、アクリル系粘着テープ又はシート
JP2012001632A (ja) * 2010-06-16 2012-01-05 Fujifilm Corp インク組成物、インクセット及び画像形成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005307198A (ja) * 2004-03-26 2005-11-04 Canon Inc 活性エネルギー線硬化型水性インク、それを用いたインクジェット記録方法、インクカートリッジ、記録ユニット及びインクジェット記録装置
JP2007277380A (ja) * 2006-04-05 2007-10-25 Canon Inc 水性活性エネルギー線硬化型インク、インクジェット記録方法及び記録物
JP2009256607A (ja) * 2008-03-17 2009-11-05 Nitto Denko Corp アクリル系粘着剤、アクリル系粘着剤層、アクリル系粘着テープ又はシート
JP2012001632A (ja) * 2010-06-16 2012-01-05 Fujifilm Corp インク組成物、インクセット及び画像形成方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017218523A (ja) * 2016-06-08 2017-12-14 株式会社リコー インク及びインクカートリッジ
EP3909782A1 (fr) * 2020-05-14 2021-11-17 Ricoh Company, Ltd. Dispositif et procédé de formation d'images

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