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WO2017212848A1 - Procédé d'enregistrement à jet d'encre - Google Patents

Procédé d'enregistrement à jet d'encre Download PDF

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Publication number
WO2017212848A1
WO2017212848A1 PCT/JP2017/017539 JP2017017539W WO2017212848A1 WO 2017212848 A1 WO2017212848 A1 WO 2017212848A1 JP 2017017539 W JP2017017539 W JP 2017017539W WO 2017212848 A1 WO2017212848 A1 WO 2017212848A1
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WO
WIPO (PCT)
Prior art keywords
ink
pigment
acid
mgkoh
amine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/017539
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English (en)
Japanese (ja)
Inventor
晴加 森山
恒 森
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to JP2018522378A priority Critical patent/JPWO2017212848A1/ja
Publication of WO2017212848A1 publication Critical patent/WO2017212848A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink

Definitions

  • the present invention relates to an ink jet recording method, and more particularly to an ink jet recording method capable of achieving both prevention of image bleeding and cracking.
  • Patent Document 1 as a method of forming an image without bleeding on a non-ink-absorbing recording medium, a recording medium provided with a treatment liquid containing a resin and an aggregating agent is used with an ink containing a pigment, an anionic pigment dispersant, and water. Forming an image is disclosed.
  • Patent Document 1 when a film base material is used as a non-ink-absorbing recording medium, the ink does not penetrate into the base material, so the entire amount of ink must be dried after printing. During this drying, the image shrinks due to a large change in volume of the ink, and the image may crack. In particular, it has been found that cracks become prominent when the treatment liquid contains a highly polar resin. That is, the technology of Patent Document 1 has found room for further improvement from the viewpoint of achieving both prevention of image bleeding and cracking.
  • an object of the present invention is to provide an ink jet recording method capable of achieving both prevention of image bleeding and cracking.
  • the above problems are solved by the following inventions. 1. On a low water-absorbing recording medium provided with a treatment liquid containing at least a resin and a flocculant, When recording using an inkjet ink containing at least a pigment, a pigment dispersant, an organic solvent, and water, One or a plurality of pigment dispersants contained in the ink-jet ink have an acid value and an amine value as a whole. 2.
  • the ink jet recording method according to 1 above which comprises one or more pigment dispersants having an acid value in the range of 60 mgKOH / g or more and 200 mgKOH / g or less as the one or plural pigment dispersants contained in the ink jet ink. . 3.
  • One or a plurality of pigment dispersants contained in the inkjet ink has an amine / acid ratio X represented by the following formula (1) in the range of 0.1 or more and 2 or less.
  • X (B V1 ⁇ B C1 + B V2 ⁇ B C2 +... + B Vm ⁇ B Cm ) / (A V1 ⁇ A C1 + A V2 ⁇ A C2 +...
  • each of the m kinds of pigment dispersants having at least an amine value (mgKOH / g) has an amine value (mg KOH / g) of B V1 to B Vm , and each concentration (% by weight with respect to the total amount of the ink-jet ink) of B C1 to Let B Cm .
  • each of the n kinds of pigment dispersants having at least an acid value (mgKOH / g) is represented by A V1 to A Vn
  • each concentration (% by weight with respect to the total amount of the inkjet ink) is represented by A C1 to A Cn .
  • m and n are each an integer of 1 or more. ] 4).
  • the acidic flocculant of the treatment liquid is an organic acid. 7).
  • an ink jet recording method capable of achieving both prevention of image bleeding and cracking.
  • a pigment, a pigment dispersant, an organic solvent and water are added onto a low water-absorbing recording medium (hereinafter also simply referred to as a recording medium) to which a treatment liquid containing at least a resin and a flocculant is applied.
  • Recording is performed using at least an inkjet ink (hereinafter also simply referred to as ink).
  • ink an inkjet ink
  • one or more kinds of pigment dispersants contained in the ink have an acid value and an amine value as a whole.
  • the effect of achieving both prevention of image bleeding and prevention of cracks can be obtained.
  • the ink components recorded (applied) on the low water-absorbing recording medium are aggregated by the components of the treatment liquid applied in advance on the recording medium.
  • the pigment dispersant contained in the ink has an acid value
  • the anionic sites in the pigment dispersant are lost due to the action of the flocculant, which is a component of the treatment liquid, and aggregation occurs. Thereby, blurring of the image is prevented.
  • the pigment dispersant since the pigment dispersant has an amine value, a cationic site is generated in the pigment dispersant when the flocculant acts. Then, the generated cationic sites repel each other, thereby preventing the above-described excessive progress of aggregation. Thereby, shrinkage of the image is suppressed and cracking of the image is also prevented.
  • the cation moiety can interact with the anion moiety. Therefore, when the amount of ink applied is relatively large with respect to the amount of the flocculant (for example, when the printing rate is increased), even if the anion portion is not completely eliminated by the flocculant, Aggregation proceeds by the interaction, and blurring of the image can be effectively prevented.
  • ⁇ Low water absorption recording medium> A low water-absorbing recording medium to be recorded by an ink jet recording method is prepared.
  • low water-absorbing recording media examples include low-water-absorbing recording media such as gravure and coated paper for offset printing, and film, plastic board, glass, tile, etc. And non-water-absorbing recording media such as rubber.
  • the plastic board examples include soft vinyl chloride, hard vinyl chloride, an acrylic board, and a polyolefin plastic board.
  • non-water-absorbing films examples include known plastic films.
  • specific examples of known plastic films include polyester films including polyethylene terephthalate, etc .; polyolefin films including polyethylene films, polypropylene films, etc .; polyamide films including nylon, etc .; polystyrene films; polyvinyl chloride films; polycarbonate films; A biodegradable film including a polylactic acid film and the like.
  • a film coated with polyvinylidene chloride on one side or both sides, or a film deposited with a metal oxide can be preferably used. The film is used as a film substrate.
  • the non-water-absorbing film may be an unstretched film or a stretched film.
  • non-water-absorbing film that has been subjected to anti-fogging processing can also be preferably used.
  • examples of the film subjected to the antifogging process include a film containing a surfactant.
  • the surface of the non-water-absorbing film is preferably surface-treated by corona discharge or ozone treatment.
  • the treatment liquid applied on the low water-absorbing recording medium contains at least a resin and a flocculant.
  • the resin is not particularly limited, and examples thereof include olefin resins, urethane resins, acrylic resins, urethane-acrylic hybrid resins, polyvinyl alcohol, polyethyleneimine, and polyallylamine.
  • urethane resin as the resin, it is possible to improve the adhesion of an image recorded by the ink jet method described later. Further, by using a urethane resin, the flexibility of the base material after image recording is not easily lost when a flexible base material such as a film base material is used as the low water-absorbing recording medium.
  • the recording medium is composed of a low-polarity film substrate such as a stretched polyolefin film, for example, a stretched polypropylene film (abbreviated as OPP), the adhesion of an image recorded by an ink jet method described later is improved.
  • a urethane resin having a low polarity mixed with the urethane resin rather than using the urethane resin alone.
  • a cationic or nonionic resin can be preferably used from the viewpoint of improving the dispersibility of the flocculant, and a cationic resin is particularly preferable.
  • Examples of commercially available products containing urethane resins include “Yuriano W600”, “Yuriano KL-422” and “Yuriano W321” (“Yuriano” is a registered trademark of the company) manufactured by Arakawa Chemical Industries, Daiichi Kogyo Seiyaku Co., Ltd.
  • Examples of commercially available products containing urethane-acrylic hybrid resins include “Acryt WEM-505c” and “Acryt WEM-506c” (“Acryt” is a registered trademark of the company) manufactured by Taisei Fine Chemical Co., Ltd., manufactured by Ohara Palladium Chemical Co., Ltd. "Palacon PJ-S2", “T-GN133", “SE2202” and “WS4030” manufactured by Seiko PMC, and “Polymaron 360” (“Polymalon” is a registered trademark of the company) manufactured by Arakawa Chemical Industries, etc. It is done.
  • Examples of commercially available products containing acrylic resins include “RKW-620” and “AKW-107” manufactured by Taisei Fine Chemical Co., Ltd.
  • Examples of commercially available products containing olefin-based resins include “Arrow Base CB-1200” and “Arrow Base DC-1200” (“Arrow Base” is a registered trademark of the company) manufactured by Unitika, and “ E-415 ”,“ E-480T ”,“ AE-301 ”,“ AE-202 ”,“ AE-502 ”and the like.
  • the resin is preferably contained in the treatment liquid as resin fine particles.
  • the volume average particle diameter of the resin fine particles is preferably in the range of 10 nm to 10 ⁇ m.
  • the volume average particle size can be measured by a commercially available particle size measuring instrument using dynamic light scattering method, electrophoresis method, etc., but the measurement by dynamic light scattering method is simple and the particle size region. Can be measured accurately.
  • the resin content in the treatment liquid is preferably in the range of 5% by weight to 40% by weight and more preferably in the range of 10% by weight to 30% by weight with respect to the weight of the treatment liquid.
  • Processing resin may be used alone or in combination of two or more.
  • Flocculant As the aggregating agent, those capable of aggregating ink components are used, and in particular, those capable of aggregating by acting on the carboxy group constituting the acid value of the pigment dispersant in the ink can be preferably used.
  • acids As specific examples of the flocculant, acids, acidic polymers, polyvalent metal salts, cationic polymers and the like can be preferably exemplified.
  • the acid and acidic polymer can aggregate the pigment by aggregating the pigment dispersant having an acid value (having an anionic group) in the ink due to pH fluctuation or the like.
  • the acid may be either an inorganic acid or an organic acid.
  • inorganic acids include orthophosphoric acid, phosphorous acid, hypophosphorous acid, nitric acid, nitrous acid, sulfuric acid, hydrochloric acid and the like.
  • organic acid include formic acid, acetic acid, propionic acid, isobutyric acid, oxalic acid, fumaric acid, malic acid, citric acid, malonic acid, succinic acid, maleic acid, benzoic acid, 2-pyrrolidone-5-carboxylic acid, Examples thereof include lactic acid, acrylic acid or a derivative thereof, methacrylic acid or a derivative thereof, acrylamide or a derivative thereof, and a sulfonic acid derivative.
  • the acidic polymer examples include polyacrylic acid or a derivative thereof, polymethacrylic acid or a derivative thereof, polyacrylamide or a derivative thereof, polysulfonic acid or a derivative thereof, polyphosphoric acid or a derivative thereof, and the like.
  • the acid and acidic polymer may be neutralized, but those that are unneutralized or partially neutralized can be used more preferably.
  • an acidic flocculant such as an acid or an acidic polymer from the viewpoint of promptly aggregating.
  • acids are preferred, and organic acids are most preferred.
  • organic acid compatibility with other components such as a resin constituting the treatment liquid can be improved, and further, since the salt is hardly formed when the treatment liquid is dried, an effect of excellent transparency can be obtained.
  • the polyvalent metal salt can agglomerate with the pigment dispersant having an acid value (having an anionic group) in the ink by salting out or the like to aggregate the pigment.
  • a metal salt having a valence of 2 or more can be used as the polyvalent metal salt.
  • the type of metal (cation) constituting the polyvalent metal salt is not particularly limited.
  • divalent metal ions such as Ca 2+ , Cu 2+ , Ni 2+ , Mg 2+ , Zn 2+ and Ba 2+ , Al 3+ , Fe 3+
  • trivalent metal ions such as Cr 3+ and Y 3+ and tetravalent metal ions such as Zr 4+ .
  • the type of the salt constituting the polyvalent metal salt is not particularly limited, and for example, known salts such as carbonate, sulfate, nitrate, hydrochloride, organic acid salt, borate, and phosphate can be used. It may be a salt corresponding to the acid.
  • Specific examples of the polyvalent metal salt include calcium acetate and calcium chloride.
  • the cationic polymer can agglomerate with a pigment dispersant having an acid value (having an anionic group) in the ink by salting out to aggregate the pigment.
  • a pigment dispersant having an acid value (having an anionic group) in the ink by salting out to aggregate the pigment.
  • a polymer having a primary to quaternary amine can be preferably used.
  • the cationic polymer may be neutralized or not neutralized.
  • the cationic polymer can be obtained as a commercial product, and examples thereof include “polyallylamine” manufactured by Nittobo Medical Co., Ltd.
  • flocculant of the treatment liquid one kind may be used alone, or plural kinds may be used in combination.
  • the content of the flocculant with respect to 100 parts by weight of the resin in the treatment liquid is preferably in the range of 1 to 50 parts by weight, and more preferably in the range of 5 to 30 parts by weight.
  • the treatment liquid can contain a solvent.
  • the solvent is not particularly limited, for example, water can be used.
  • an organic solvent may be included as a solvent.
  • the solvent can be removed by drying after coating.
  • the treatment liquid can contain a surfactant.
  • the method of applying the treatment liquid to the low water-absorbing recording medium is not particularly limited, and preferred examples include a roller coating method, a curtain coating method, a spray coating method, and an ink jet method.
  • drying treatment for drying the solvent in the treatment liquid.
  • the drying method is not particularly limited, drying with warm air, drying with a heater, or the like can be used. In this way, a film can be formed on the surface of the recording medium.
  • the amount of the resin in the coating is preferably in the range of 0.5 g / m 2 to 5 g / m 2 . Further, the amount of the flocculant in the coating is preferably in the range of 0.1 g / m 2 or more and 1 g / m 2 or less.
  • the thickness of the coating after drying is not particularly limited, for example, it is preferably in the range of 0.1 ⁇ m to 4 ⁇ m. Thereby, it is possible to suitably prevent the texture of the recording medium from changing, and a sufficient amount of the flocculant can be contained in the coating film.
  • the present invention is characterized in that one or more pigment dispersants contained in the ink have an acid value and an amine value as a whole, one or more pigment dispersants having an acid value, and one or more pigment dispersants having an amine value.
  • the pigment dispersant as a whole can have an acid value and an amine value by appropriately combining the pigment dispersant from among the above pigment dispersants and one or more pigment dispersants having an acid value and an amine value.
  • the acid value and amine value can be measured by potentiometric titration, for example, by the method described in Color Material Association Journal 61, [12] 692-698 (1988). “Having an acid value” or “having an amine value” means that these values are not zero.
  • A Combined use of a pigment dispersant having an acid value and not having an amine value and a pigment dispersant having an amine value and not having an acid value
  • a pigment having an acid value and having no amine value Combined use of a dispersant and a pigment dispersant having an acid value and an amine value
  • c Combined use of a pigment dispersant having an amine value and no acid value, and a pigment dispersant having an acid value and an amine value
  • D Single use of pigment dispersant with acid value and amine value
  • pigment dispersants having an acid value and an amine value
  • the configuration (b), (c) or (d) is preferable.
  • a pigment dispersant having an acid value in the range of 60 mgKOH / g to 200 mgKOH / g can be preferably used.
  • the acid value in one molecule of the pigment dispersant is 60 mgKOH / g or more, the aggregation is prevented from proceeding too quickly, and the ink applied to the base material spreads appropriately. As a result, the ink dot diameter can be sufficiently ensured, the coalescence with the adjacent ink dots proceeds suitably, and the occurrence of streaks is prevented. Further, when the acid value in one molecule of the pigment dispersant is 200 mgKOH / g or less, aggregation is prevented from proceeding too slowly, and the ink applied to the substrate can be prevented from spreading. Thereby, it is possible to further prevent bleeding of the image.
  • the pigment dispersant having an acid value preferably has an alkali-neutralized anionic group.
  • the alkali-neutralized anionic group preferably include an alkali-neutralized carboxyl group and a sulfonic acid group.
  • alkali neutralization Preferred are carboxyl groups.
  • alkali that neutralizes the anionic group examples include metal base compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide, organic amines such as ammonia, triethylamine, pyridine, morpholine, and monoethanol.
  • metal base compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide
  • organic amines such as ammonia, triethylamine, pyridine, morpholine, and monoethanol.
  • alkanolamines such as amines.
  • an acrylic dispersant can be preferably used.
  • the acrylic dispersant one or more selected from poly (meth) acrylic acid and (meth) acrylic acid copolymers can be suitably used.
  • the acrylic dispersant contains (meth) acrylic acid as a monomer component.
  • an acrylic dispersant a copolymer of (meth) acrylic acid (ie, poly (meth) acrylic acid) or a copolymer obtained by copolymerizing other monomer components such as styrene as needed (ie, (meth)) (Acrylic acid copolymer) can be preferably used.
  • the pigment dispersant having an acid value can be obtained as a commercial product.
  • DISPERBYK-102 “DISPERBYK-190”, “DISPERBYK-194”, “DISPERBYK-2090”, “DISPERBYK-” manufactured by Big Chemie “2091”, “DISPERBYK-2095”, “DISPERBYK-2096”, “Joncrill 67”, “Johncrill 690”, “Johncrill 819”, “Johncrill 683”, “PDX-6102B”, “SFX” manufactured by BASF “JDX-6180”, “JDK-6500”, “EFKA6230” (John Krill is a registered trademark of the company), and the like.
  • the amine value of the pigment dispersant having an amine value is not particularly limited.
  • a pigment dispersant having an amine value of 10 mgKOH / g or more and 200 mgKOH / g or less can be used.
  • the pigment dispersant having an amine value includes, for example, amino-substituted styrene, amino-substituted styrene having 1 or 2 alkyl groups having 1 to 4 carbon atoms, vinylpyridine or a salt thereof, and 1 to 4 carbon atoms as monomer components.
  • An ethylenically unsaturated amino monomer selected from the group consisting of alkyl group-substituted vinylpyridines or salts thereof, vinylimidazole or salts thereof, and alkyl group-substituted imidazoles having 1 to 4 carbon atoms or salts thereof. it can.
  • a pigment dispersant having an amine value can be obtained as a commercial product, for example, “DISPERBYK-109”, “DISPERBYK-108”, “DISPERBYK-164”, “DISPERBYK-2008”, “DISPERBYK-” manufactured by BYK Chemie. 2050 ",” DISPERBYK-2055 “,” DISPERBYK-2155 “, and” EFKA4570 "manufactured by BASF.
  • a pigment dispersant having an acid value and an amine value a pigment dispersant having an acid value in the range of 60 mgKOH / g to 200 mgKOH / g can be preferably used.
  • the amine value is not particularly limited.
  • a pigment dispersant having an amine value of 10 mgKOH / g or more and 200 mgKOH / g or less can be used.
  • the pigment dispersant having an acid value and an amine value can contain the monomer components exemplified for the pigment dispersant having an acid value and the pigment dispersant having an amine value.
  • Pigment dispersants having an acid value and an amine value can be obtained as commercial products.
  • “DISPERBYK-180”, “DISPERBYK-191”, “DISPERBYK-187”, “DISPERBYK-2010” manufactured by Big Chemie examples thereof include “DISBYK”, “DISPERBYK-140”, “DISPERBYK-2001”, “EFKA5071”, “EFKA4510”, “EFKA4530”, “EFKA4570”, “EFKA6220”, and “EFKA6225” manufactured by BASF.
  • the one or more pigment dispersants contained in the ink preferably have an amine / acid ratio X represented by the following formula (1) in the range of 0.1 to 2, preferably 0.3 to 1.5. The following range is more preferable.
  • each of the m kinds of pigment dispersants having at least an amine value is represented by B V1 to B Vm and each concentration (% by weight with respect to the total amount of ink) is represented by B C1 to B Cm
  • the acid values (mgKOH / g) of n kinds of pigment dispersants having at least an acid value are A V1 to A Vn and the respective concentrations (% by weight with respect to the total amount of ink) are A C1 to A Cn .
  • m and n are each an integer of 1 or more.
  • the crack preventing property is more remarkably exhibited. Further, when the amine / acid ratio X is 2 or less, and further 1.5 or less, the bleeding prevention property is more remarkably exhibited.
  • the pigment dispersant of the ink may further include a pigment dispersant having neither an acid value nor an amine value in addition to the pigment dispersant described above.
  • the content of the pigment dispersant in the ink is preferably in the range of 10 to 100 parts by weight, more preferably in the range of 10 to 50 parts by weight with respect to 100 parts by weight of the pigment. .
  • pigments to be included in the ink conventionally known pigments can be used without particular limitation, and any of water-dispersible pigments, solvent-dispersible pigments and the like can be used.
  • organic pigments such as insoluble pigments and lake pigments, or oxidation pigments can be used.
  • Inorganic pigments such as titanium and carbon black can be preferably used. These pigments can be used in the state of being dispersed in the ink by the above-described pigment dispersant.
  • Insoluble pigments are not particularly limited, for example, azo, azomethine, methine, diphenylmethane, triphenylmethane, quinacridone, anthraquinone, perylene, indigo, quinophthalone, isoindolinone, isoindoline, azine, oxazine, thiazine, dioxazine, thiazole, phthalocyanine , Diketopyrrolopyrrole and the like are preferable.
  • the organic pigment is not particularly limited, but the following can be preferably exemplified.
  • pigments used for yellow or orange include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 15: 3, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 138, C.I. I. And CI Pigment Yellow 155.
  • pigments used for magenta or red include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I.
  • Pigment red 166 C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 202, C.I. I. Pigment red 222, C.I. I. Pigment violet 19 and the like.
  • pigments used for cyan or green include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. And CI Pigment Green 7.
  • pigments used for black and the like include C.I. I. Pigment black 1, C.I. I. Pigment black 6, C.I. I. Pigment black 7 and the like.
  • the weight average particle diameter of the dispersed state of the pigment in the ink is preferably in the range of 50 nm to 200 nm. Thereby, the dispersion stability of the pigment can be improved, and the storage stability of the ink can be improved.
  • the particle size of the pigment can be determined by a commercially available particle size measuring instrument using a dynamic light scattering method, an electrophoresis method, etc., but the measurement by the dynamic light scattering method is simple and the particle size region is Accurate measurement.
  • the pigment can be used after being dispersed by a disperser together with a pigment dispersant and other additives necessary for various desired purposes.
  • the disperser a conventionally known ball mill, sand mill, line mill, high-pressure homogenizer, or the like can be used. Among them, it is preferable to disperse the pigment by a sand mill because the particle size distribution becomes sharp.
  • the material of the beads used for sand mill dispersion is not particularly limited, but zirconia or zircon is preferable from the viewpoint of preventing generation of bead fragments and contamination of ionic components. Further, the bead diameter is preferably 0.3 mm to 3 mm.
  • the pigment content in the ink is not particularly limited.
  • the inorganic pigment is preferably in the range of 7 to 18% by weight, and the organic pigment is in the range of 0.5 to 7% by weight. It is preferable.
  • Organic solvent As the organic solvent to be included in the ink, a water-soluble organic solvent is preferably used.
  • monohydric alcohols, glycols (dihydric alcohols), trihydric alcohols, glycol ethers, acetates, amines, amides are used. Examples are preferable.
  • Preferred examples of monohydric alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, and tertiary butanol.
  • glycols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having 5 or more ethylene oxide groups, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and propylene oxide groups.
  • Polypropylene glycol, butylene glycol, thiodiglycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,2-hexanediol 1,2-heptanediol, 3-methyl-2,4-pentanediol and the like can be preferably exemplified.
  • trivalent alcohols include glycerin and hexanetriol.
  • glycol ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, Triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipro Lenglycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether
  • acetates include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol diacetate and the like.
  • amines include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, Preferred examples include pentamethyldiethylenetriamine and tetramethylpropylenediamine.
  • amides include 2-pyrrolidinone, dimethylimidazolidinone, formamide, N, N-dimethylformamide, N, N-dimethylacetamide and the like.
  • solvents may be used alone or in combination of two or more.
  • the ink preferably contains a surfactant in order to improve dischargeability and wettability.
  • the surfactant is not particularly limited, and examples thereof include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant.
  • Preferred examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.
  • anionic surfactant examples include fatty acid soap, N-acyl-N-methylglycine salt, N-acyl-N-methyl- ⁇ -alanine salt, N-acyl glutamate, acylated peptide, alkyl sulfonic acid Salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl sulfoacetate, ⁇ -olefin sulfonate, N-acylmethyl taurine, sulfated oil, higher alcohol sulfate, secondary Higher alcohol sulfate, alkyl ether sulfate, secondary higher alcohol ethoxysulfate, polyoxyethylene alkylphenyl ether sulfate, monoglyculate, fatty acid alkylolamide sulfate, alkyl ether phosphate ester, alkyl Preferred examples include phosphate ester salts.
  • amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine and the like.
  • nonionic surfactant examples include polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene.
  • Glycerin fatty acid ester polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, fatty acid alkanol Amides, polyoxyethylene fatty acid amides, polyoxyethylene alkylamines, alkylamines Kisaido, acetylene glycol, acetylene alcohol can be preferably exemplified.
  • surfactants may be used alone or in combination of two or more.
  • the content of the surfactant in the ink is not particularly limited, but is preferably in the range of 0.1% by weight to 5.0% by weight.
  • Inkjet method using a printer including an ink jet head loaded with the ink described above, ink is ejected as droplets from the nozzle of the ink jet head based on a digital signal, and this is used as a treatment liquid in the above-described low water absorption recording medium. It is possible to record an image by landing on the area coated with.
  • the inkjet head may be either an on-demand system or a continuous system.
  • an electro-mechanical conversion method for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a sheared wall type, etc.
  • an electro-thermal conversion method for example, any system such as a thermal ink jet type or a bubble jet (registered trademark) type may be used.
  • an ink jet head (also referred to as a piezo ink jet head) using a piezoelectric element as the electro-mechanical conversion element used in the electro-mechanical conversion system is suitable.
  • Inkjet printers have two printing methods called a scanning method (also called a multi-pass method) and a single-pass method.
  • the scanning method is a method in which, for example, the head carriage is reciprocated in the horizontal direction (main scanning direction) with respect to the film conveyance direction (sub-scanning direction), and the image is completed by a plurality of passes. Although slow, the number of heads used can be reduced.
  • the single pass method is a method in which, for example, a line head type ink jet head (head carriage) is fixed, and an image is completed by a single pass on the paper being transported. Sex is obtained.
  • the conveyance speed in the main scanning direction is about several meters / minute (more specifically, 1 m / minute to 5 meters / minute), but in the single-pass method, it is several tens of meters / minute (more specifically, 10 meters). / Min. To 100 m / min) can be printed.
  • the ink adhesion amount per unit time may be ten times or more that of the scan method in the single pass method.
  • the amount of ink applied or the amount of ink attached per second becomes relatively large. Even if a large amount of an aggregating agent is used in accordance with this, the pigment dispersant has an amine value as well as an acid value as in the ink according to the present invention, thereby preventing the agglomeration from proceeding excessively. , Cracking is prevented.
  • the cation site resulting from the amine value can interact with the anion site in the pigment dispersant, the anion site is caused by the flocculant when the amount of ink applied is relatively large relative to the amount of the flocculant. Even if it is not completely disappeared, aggregation proceeds due to interaction with the cation site, and blurring of the image can be effectively prevented. Thereby, the single path method can be advantageously applied.
  • the line head type ink jet head refers to an ink jet head having a length longer than the width of the printing range.
  • a single head having a width larger than the print range may be used, or a plurality of heads may be combined so as to be larger than the width of the print range. It is also preferable to arrange a plurality of heads side by side so that the nozzles are arranged in a staggered manner, thereby increasing the resolution of the heads as a whole.
  • a maintenance operation for discharging ink from the nozzles can be executed.
  • This operation can be executed in a state where the ink jet head is moved out of the region on the recording medium (that is, a state where ink is not applied to the recording medium).
  • the inkjet head can be easily moved out of the region on the recording medium by scanning.
  • the single pass method since the inkjet head is usually fixed, it is relatively difficult to move out of the area on the recording medium.
  • the ink can be suitably imparted with the property that nozzle clogging is unlikely to occur even when dried, so the burden of ink discharge can be reduced and the ejection stability is high. Therefore, from this point of view, the single path method can be advantageously applied.
  • the ink jet recording method of the present invention can be suitably used for various applications for recording on a recording medium comprising a film substrate by the ink jet method.
  • the use of the recording medium on which recording is performed by the inkjet recording method of the present invention is not particularly limited. Specific examples of the use of the recorded recording medium include, for example, a packaging film for packaging food, beverages, and the like.
  • Example 1 Preparation of treatment liquid Cationic urethane resin R-1 (“JK-870” manufactured by Meisei Chemical Industry Co., Ltd.) as a resin and malonic acid as a flocculant were added to a solvent comprising water while stirring, and 5.0 ⁇ m The solution was filtered through a filter.
  • Cationic urethane resin R-1 (“JK-870” manufactured by Meisei Chemical Industry Co., Ltd.) as a resin and malonic acid as a flocculant
  • the average particle size of the pigment particles contained in this pigment dispersion was 113 nm.
  • the average particle size was measured by “Zeta Sizer 1000HS” manufactured by Marul Balloon.
  • ethylene glycol as the organic solvent
  • silicon nonionic surfactant (“Silface SAG503A” manufactured by Nissin Chemical Industry Co., Ltd.)
  • ion-exchanged water as the surfactant are added to the obtained pigment dispersion while stirring. And it filtered with a 1 micrometer filter, and obtained the ink.
  • treatment liquid obtained as described above was applied to a film substrate (biaxially stretched polypropylene film (“FOS # 60” manufactured by Phutamura Chemical Co., Ltd.)) with a wire bar and dried with a hot air dryer at 80 ° C. A film was formed.
  • the amount of cationic urethane resin in the coating is 1.6 g / m 2 and the amount of malonic acid is 0.3 g / m 2 .
  • Ink application (inkjet recording)
  • Two independent drive heads of Konica Minolta's piezo-type inkjet head (360 dpi, discharge amount 14 pL) are arranged so that the nozzles are staggered, a head module of 720 dpi ⁇ 720 dpi is created, and it is moved in the transport direction on the stage transporter
  • the nozzle rows were installed so as to be orthogonal.
  • another head module was installed side by side in the transport direction so that ink-jet print images for two colors could be printed by the one-pass method.
  • Both of the head modules for two colors are loaded with the ink obtained as described above, and a solid ink is applied on the film base film transported by the stage transporter with an ink application amount of 22.5 cc / m 2 by the one-pass method.
  • An ink jet recording apparatus was configured so that printing was possible.
  • ink was solid-printed at an ink application amount of 22.5 cc / m 2 on a square area of 5 cm in length and width on the film base film, and then 15 ° C. at 60 ° C. on a hot plate. Partial drying was performed to form a solid image.
  • Evaluation method Bleeding prevention property The obtained images were evaluated for the bleeding prevention property according to the following evaluation criteria. ⁇ Evaluation criteria> AA: No bleeding is observed even when enlarged with a loupe. A: Smear is observed when magnified with a magnifying glass, but is not visually observed. B: Although blur can be discerned visually, there is no practical problem. C: Severe blurring and not practical.
  • Example 1 it was confirmed that slight streaks occurred in the image.
  • DISPERBYK-2090 manufactured by Big Chemie
  • Example 5 (Example 5)
  • the image was formed in the same manner as in Example 1 except that the blending amount was adjusted so that The results evaluated in the same manner as in Example 1 are shown in Table 1.
  • Example 6 (Example 6)
  • the image was formed in the same manner as in Example 1 except that the blending amount was adjusted so that The results evaluated in the same manner as in Example 1 are shown in Table 1.
  • Example 9 In Example 8, an image was formed in the same manner as in Example 8, except that calcium acetate was used instead of malonic acid as the coagulant for the treatment liquid. The results evaluated in the same manner as in Example 1 are shown in Table 1.
  • Example 1 (Comparative Example 1)
  • the results evaluated in the same manner as in Example 1 are shown in Table 1.
  • Comparative Example 2 In Comparative Example 1, as the resin of the treatment liquid, cationic urethane resin R-1 (“JK-870” manufactured by Meisei Chemical Co., Ltd.) and olefin resin R-2 (“E-415” manufactured by Nippon Paper Industries Co., Ltd.) was used in the same manner as in Comparative Example 1 except that the blending amount was adjusted so as to be the amount shown in Table 1. The results evaluated in the same manner as in Example 1 are shown in Table 1.
  • Comparative Example 4 In Comparative Example 1, an image was formed in the same manner as Comparative Example 1 except that the blending of the flocculant was omitted. The results evaluated in the same manner as in Example 1 are shown in Table 1.
  • Comparative Example 5 In Comparative Example 1, an image was formed in the same manner as Comparative Example 1 except that the blending of the resin of the treatment liquid was omitted. The results evaluated in the same manner as in Example 1 are shown in Table 1. In Comparative Example 5, the flocculant deposited by drying of the treatment liquid was not worthy of evaluation.
  • Comparative Example 1 in which a highly polar resin R-1 (cationic urethane resin) is used alone and Comparative Example in which a part of the resin R-1 is replaced with a low polarity resin R-2 (olefin resin) From comparison with 2, it can be seen that cracking is promoted by the influence of the highly polar resin R-1.
  • Examples 1 to 15 although a highly polar resin R-1 was used under the same conditions as in Comparative Example 1, cracks were prevented, so a remarkable effect was confirmed. it can.
  • Examples 1 to 5 by including one or more pigment dispersants having an acid value in the range of 60 mgKOH / g or more and 200 mgKOH / g or less, generation of streaks is prevented, and image bleeding is preferable. It can be seen that it can be prevented.

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

Abstract

L'invention concerne un procédé d'enregistrement à jet d'encre qui est susceptible d'obtenir un bon équilibre entre la prévention de floutage et la prévention de fissuration d'images. L'invention concerne un procédé d'enregistrement à jet d'encre dans lequel, lorsque l'enregistrement est réalisé sur un support d'enregistrement à faible absorption d'eau, sur lequel un liquide de traitement contenant au moins une résine et un floculant a été appliqué, à l'aide d'une encre à jet d'encre contenant au moins un pigment, un dispersant de pigment, un solvant organique et de l'eau, un ou plusieurs dispersants de pigment contenus dans l'encre à jet d'encre ont un indice d'acide et un indice d'amine dans l'ensemble. De préférence, un ou plusieurs dispersants de pigment ayant un indice d'acide dans la plage allant de 60 mgKOH/g à 200 mgKOH/g (inclus) sont contenus sous la forme d'un ou plusieurs dispersants de pigment contenus dans l'encre à jet d'encre.
PCT/JP2017/017539 2016-06-07 2017-05-09 Procédé d'enregistrement à jet d'encre Ceased WO2017212848A1 (fr)

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Cited By (8)

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JP2019126909A (ja) * 2018-01-22 2019-08-01 株式会社リコー 記録方法、及び記録装置
JP2020059810A (ja) * 2018-10-11 2020-04-16 コニカミノルタ株式会社 インクジェット記録液セット、インクジェット記録用前処理液の製造方法、印刷物及びインクジェット記録方法
JPWO2022014454A1 (fr) * 2020-07-15 2022-01-20
US20220073775A1 (en) * 2019-05-17 2022-03-10 Fujifilm Corporation Pretreatment liquid for impermeable base material, ink set, image recording method, image recorded material, and recording medium and method of producing same
CN115103885A (zh) * 2020-02-28 2022-09-23 富士胶片株式会社 油墨组合物、油墨组及图像记录方法
JP2023171600A (ja) * 2017-12-18 2023-12-01 デュポン エレクトロニクス インコーポレイテッド オフセット媒体上に印刷するためのインク液セット
US12344753B2 (en) 2020-02-28 2025-07-01 Fujifilm Corporation Ink set and image recording method
WO2025154438A1 (fr) * 2024-01-15 2025-07-24 コニカミノルタ株式会社 Ensemble encres, procédé d'impression à jet d'encre et dispositif d'enregistrement

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JP2002019263A (ja) * 2000-07-11 2002-01-23 Seiko Epson Corp インクジェット記録方法
JP2009013394A (ja) * 2007-06-08 2009-01-22 Fujifilm Corp インク組成物、インクセット、及びインクジェット記録方法

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JP2002019263A (ja) * 2000-07-11 2002-01-23 Seiko Epson Corp インクジェット記録方法
JP2009013394A (ja) * 2007-06-08 2009-01-22 Fujifilm Corp インク組成物、インクセット、及びインクジェット記録方法

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023171600A (ja) * 2017-12-18 2023-12-01 デュポン エレクトロニクス インコーポレイテッド オフセット媒体上に印刷するためのインク液セット
JP2019126909A (ja) * 2018-01-22 2019-08-01 株式会社リコー 記録方法、及び記録装置
JP7069741B2 (ja) 2018-01-22 2022-05-18 株式会社リコー 記録方法、及び記録装置
JP2020059810A (ja) * 2018-10-11 2020-04-16 コニカミノルタ株式会社 インクジェット記録液セット、インクジェット記録用前処理液の製造方法、印刷物及びインクジェット記録方法
JP7192376B2 (ja) 2018-10-11 2022-12-20 コニカミノルタ株式会社 インクジェット記録液セット、インクジェット記録用前処理液の製造方法、印刷物及びインクジェット記録方法
US20220073775A1 (en) * 2019-05-17 2022-03-10 Fujifilm Corporation Pretreatment liquid for impermeable base material, ink set, image recording method, image recorded material, and recording medium and method of producing same
CN115103885A (zh) * 2020-02-28 2022-09-23 富士胶片株式会社 油墨组合物、油墨组及图像记录方法
US12344753B2 (en) 2020-02-28 2025-07-01 Fujifilm Corporation Ink set and image recording method
JPWO2022014454A1 (fr) * 2020-07-15 2022-01-20
WO2022014454A1 (fr) * 2020-07-15 2022-01-20 山陽色素株式会社 Encre aqueuse pour jet d'encre et procédé permettant d'imprimer une structure fibreuse au moyen d'un système à jet d'encre
WO2025154438A1 (fr) * 2024-01-15 2025-07-24 コニカミノルタ株式会社 Ensemble encres, procédé d'impression à jet d'encre et dispositif d'enregistrement

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