Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—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
  • C09D11/02—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
• • 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
  • 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
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

• the present disclosure relates to an active energy ray-curable ink and an image recording method.
• Patent Document 1 describes an active photocurable inkjet ink capable of forming a highly sensitive, highly flexible and strong coating film, which contains a radically polymerizable monomer as a photopolymerizable compound and is inorganic.
• An active photocurable composition containing an oxide colloid is disclosed.
• an active photocurable inkjet ink having the above-mentioned performance
• Ink ink is also disclosed.
• Patent Document 2 describes an active energy ray-curable composition which suppresses sedimentation due to aggregation of silica particles, improves intermittent ejection property and color unevenness of printed images, and has high coating film hardness and excellent wear resistance.
• the volume average particle diameter of the silica particles is 1/10 to 1/3 of the volume average particle diameter of the inorganic pigment, and the silica particles
• An active energy ray-curable composition is disclosed in which the surface is modified with a (meth) acrylate compound.
• Patent Document 1 Japanese Patent Application Laid-Open No. 2006-152064
• Patent Document 2 Japanese Patent Application Laid-Open No. 2019-157062
• an image recorded by using an active energy ray-curable ink may have a strong gloss. Therefore, the above image may have a relief feeling, may be conspicuous, and the like. However, from the viewpoint of reducing the relief feeling of the image, making the image inconspicuous, etc., it may be required that the gloss is suppressed as the quality of the image recorded by using the active energy ray-curable ink. ..
• An object of one aspect of the present disclosure is to provide an active energy ray-curable ink capable of recording an image having suppressed gloss, and an image recording method using the active energy ray-curable ink.
• An active energy ray-curable ink containing a radically polymerizable monomer, inorganic oxide particles, a photoacid generator, and a photoradical polymerization initiator.
• the average primary particle size of the inorganic oxide particles is 0.1 ⁇ m to 3.0 ⁇ m.
• ⁇ 4> The active energy ray-curable ink according to any one of ⁇ 1> to ⁇ 3>, wherein the photoacid generator is a sulfonium salt.
• ⁇ 5> The active energy ray-curable ink according to any one of ⁇ 1> to ⁇ 4>, which further contains a photocation sensitizer.
• ⁇ 6> The active energy ray-curable ink according to ⁇ 5>, wherein the photocation sensitizer is a compound containing an anthracene skeleton.
• ⁇ 7> The active energy ray according to ⁇ 5> or ⁇ 6>, wherein the content of the photocation sensitizer is 0.5% by mass to 5.0% by mass with respect to the total amount of the active energy ray-curable ink.
• Curable ink. ⁇ 8> Described in any one of ⁇ 1> to ⁇ 7>, wherein the content of the inorganic oxide particles is 0.5% by mass to 15.0% by mass with respect to the total amount of the active energy ray-curable ink.
• Active energy ray-curable ink. ⁇ 9> The active energy ray according to any one of ⁇ 1> to ⁇ 8>, wherein the mass ratio of the content of the inorganic oxide particles to the content of the photoacid generator is 0.2 to 15.0.
• Curable ink ⁇ 10>
• the total content of the inorganic oxide particles and the photoacid generator is 1.0% by mass to 17.5% by mass with respect to the total amount of the active energy ray-curable ink.
• the active energy ray-curable ink according to any one.
• the mass ratio of the total contents of the radically polymerizable monomer, the inorganic oxide particles, and the photoacid generator to the content of the photoradical polymerization initiator is 6.0 to 45.0 ⁇ 1> to The active energy ray-curable ink according to any one of ⁇ 10>.
• the radically polymerizable monomer contains at least one of a monofunctional radically polymerizable monomer and a bifunctional radically polymerizable monomer. Any one of ⁇ 1> to ⁇ 11> in which the total content of the monofunctional radically polymerizable monomer and the bifunctional radically polymerizable monomer is 50% by mass or more with respect to the total amount of the active energy ray-curable ink.
• the irradiation process of irradiating the ink film with active energy rays and Image recording method including.
• an active energy ray-curable ink capable of recording an image with suppressed gloss and an image recording method using the active energy ray-curable ink are provided.
• the numerical range represented by using “-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
• the amount of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. do.
• the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. Alternatively, it may be replaced with the value shown in the examples.
• the term "process” is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
• the combination of preferred embodiments is a more preferred embodiment.
• "light” is a concept including active energy rays such as ⁇ -rays, ⁇ -rays, electron beams, ultraviolet rays, and visible rays.
• ultraviolet rays may be referred to as "UV (Ultra Violet) light".
• (meth) acrylate is a concept including both acrylate and methacrylate
• (meth) acryloyl group is a concept including both acryloyl group and methacrylic acid group
• (meth) acrylate is included.
• “Acrylic acid” is a concept that includes both acrylic acid and methacrylic acid.
• the "image” means the entire film formed by using ink
• the “image recording” means the formation of an image (that is, a film).
• image means the formation of an image (that is, a film).
• image also includes a solid image.
• the active energy ray-curable ink of the present disclosure is an active energy ray-curable ink containing a radically polymerizable monomer, inorganic oxide particles, a photoacid generator, and a photoradical polymerization initiator.
• the active energy ray-curable ink is also simply referred to as “ink”.
• the ink of the present disclosure it is possible to record an image in which gloss is suppressed. It is considered that the reason why the above effect is exhibited is related to the fact that the ink contains a radically polymerizable monomer, an inorganic oxide particle, a photoacid generator, and a photoradical polymerization initiator. In detail, the reason why the above effect is achieved is presumed as follows.
• the ink is applied onto the recording medium and the ink is applied onto the substrate (hereinafter referred to as ink). This is done by irradiating an "ink film") with light (that is, active energy rays; the same applies hereinafter).
• ink film that is, active energy rays; the same applies hereinafter.
• the radical polymerization of the radically polymerizable monomer proceeds and the ink film is cured. As a result, an image that is a cured ink film is obtained.
• the ink of the present disclosure is applied to image recording, when the ink film is irradiated with light, not only radicals are generated in the ink film by the action of the photoradical polymerization initiator, but also the photoacid generator Acid is also generated by the action. It is considered that the generated acid causes the inorganic oxide particles in the ink film to aggregate with each other to form an agglomerate. It is considered that the gloss of the image is suppressed by the formed aggregates functioning as a matting agent.
• the region on the surface side of the ink film is the region on the recording medium side of the ink film (hereinafter, "". This is a region that is more susceptible to radical polymerization inhibition by oxygen than the region on the recording medium side). Therefore, before the curing of the entire film thickness direction of the ink film is completed, the curing of the recording medium side region of the ink film is completed, but the curing of the surface side region of the ink film is still completed. It is considered that there is no such thing. At this stage, it is considered that the inorganic oxide particles contained in the ink are likely to collect in the surface side region of the ink film.
• the inorganic oxide particles gathered in the surface side region are aggregated by the action of the acid described above to form an agglomerate. It is considered that the agglomerates formed on the surface side region of the ink film effectively exert the above-mentioned function as a matting agent, and as a result, the gloss of the image is suppressed.
• Patent Document 1 Japanese Unexamined Patent Publication No. 2006-152064 substantially contains a radically polymerizable monomer as a photopolymerizable compound, inorganic oxide particles, and a photoradical polymerization initiator.
• Ink hereinafter referred to as radically polymerizable ink R1
• a compound having an oxetane ring as a photopolymerizable compound, an epoxy compound, and inorganic oxide particles are disclosed separately from the radically polymerizable ink C1.
• an ink containing a photoacid generator hereinafter referred to as a cationically polymerizable ink C1 are disclosed.
• Patent Document 1 does not disclose an ink containing all of a radically polymerizable monomer, an inorganic oxide particle, a photoacid generator, and a photoradical polymerization initiator (that is, the ink of the present disclosure).
• the inorganic oxide particles cannot be aggregated by the acid. Since the average primary particle size of the inorganic oxide particles is small, it is considered that the inorganic oxide particles that do not form aggregates do not function as a matting agent. Therefore, it is considered that the radically polymerizable ink R1 does not have the effect of suppressing gloss as obtained by the ink of the present disclosure.
• the surface of the ink film is The phenomenon of radical polymerization inhibition by oxygen in the side region does not exist. Therefore, it is difficult to obtain the effect of forming aggregates of inorganic oxide particles concentrated on the surface side region of the ink film. Therefore, it is considered that even the cationically polymerizable ink C1 does not have the effect of suppressing gloss as obtained by the ink of the present disclosure.
• the ink of the present disclosure it is possible to record an image in which gloss is suppressed. Therefore, according to the ink of the present disclosure, it is easy to obtain an image in which the gloss difference from the recording medium is suppressed. Therefore, the ink of the present disclosure can be expected to have the effect of reducing the relief feeling of the image. Further, the ink of the present disclosure can be expected to have an effect of making an image inconspicuous. Therefore, for example, when an invisible image is recorded with the ink of the present disclosure, it can be expected that an invisible image having better invisibility can be obtained.
• the ink of the present disclosure contains at least one radically polymerizable monomer.
• a compound containing an ethylenically unsaturated group is preferable.
• a (meth) acryloyl group, a vinyl group, an allyl group, or a styryl group is preferable, and a (meth) acryloyl group or a vinyl group is more preferable.
• the radically polymerizable monomer may contain only one ethylenically unsaturated group or may contain two or more. Further, the radically polymerizable monomer may contain only one type of ethylenically unsaturated group or may contain two or more types.
• the molecular weight of the radically polymerizable monomer is preferably 280 to 1500, more preferably 280 to 1000, and even more preferably 280 to 800.
• the radically polymerizable monomer in the ink of the present disclosure may be a monofunctional radically polymerizable monomer, a bifunctional radically polymerizable monomer, or a trifunctional or higher functional radically polymerizable monomer. Further, a combination containing two or more of these may be used.
• the monofunctional radically polymerizable monomer means a radically polymerizable monomer containing only one ethylenically unsaturated group.
• the bifunctional radically polymerizable monomer means a radically polymerizable monomer containing only two ethylenically unsaturated groups.
• the trifunctional or higher functional radical polymerizable monomer means a radically polymerizable monomer containing three or more ethylenically unsaturated groups.
• the monofunctional radical-polymerizable monomer, the bifunctional radical-polymerizable monomer, and the trifunctional or higher-functional radical-polymerizable monomer may be referred to as a monofunctional monomer, a bifunctional monomer, and a trifunctional or higher-functional monomer, respectively. be.
• the radically polymerizable monomer in the ink of the present disclosure is a monofunctional monomer (for example, a monofunctional monomer (hereinafter, also simply referred to as “ejection property”) from the viewpoint of reducing the viscosity of the ink (for example, ejection property from an inkjet head when used as an inkjet ink). That is, it is preferable to contain at least one of a monofunctional radical polymerizable monomer) and a bifunctional monomer (that is, a bifunctional radical polymerizable monomer).
• a monofunctional monomer for example, a monofunctional monomer (hereinafter, also simply referred to as “ejection property”) from the viewpoint of reducing the viscosity of the ink (for example, ejection property from an inkjet head when used as an inkjet ink). That is, it is preferable to contain at least one of a monofunctional radical polymerizable monomer) and a bifunctional monomer (that is, a bifunctional radical polymerizable
• the total content of the monofunctional monomer and the bifunctional monomer with respect to the total amount of the ink is preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 55% by mass or more. It is preferably 60% by mass or more, and more preferably 60% by mass or more.
• the content of the radically polymerizable monomer in the ink of the present disclosure is preferably 50% by mass or more, more preferably 60% by mass or more, and more preferably 65% by mass or more, based on the total amount of the ink. It is more preferably 70% by mass or more, and further preferably 70% by mass or more.
• the radically polymerizable monomer in the ink of the present disclosure is used from the viewpoint of ink ejection property and image abrasion resistance.
• a trifunctional or higher functional monomer preferably a trifunctional monomer
• the total content of the monofunctional monomer, the bifunctional monomer, and the trifunctional or higher functional monomer with respect to the total amount of the ink is preferably 50% by mass or more, more preferably 60% by mass or more, 65. It is more preferably 70% by mass or more, and further preferably 70% by mass or more.
• monofunctional monomer examples include monofunctional (meth) acrylate, monofunctional (meth) acrylamide, monofunctional aromatic vinyl compound, monofunctional vinyl ether, monofunctional N-vinyl compound, and the like.
• Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
• Meta) acrylate EO-modified nonylphenol (meth) acrylate, propylene oxide-modified (hereinafter referred to as PO-modified) nonylphenol (meth) acrylate, EO-modified -2-ethylhexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo Examples thereof include penthenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (3-ethyl-3-oxetanylmethyl) (meth) acrylate, and phenoxyethylene glycol (meth) acrylate.
• Examples of the monofunctional (meth) acrylamide include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, Nn-butyl (meth) acrylamide, and the like.
• Examples thereof include (meth) acrylamide, (meth) acryloylmorpholin, and the like.
• Examples of the monofunctional aromatic vinyl compound include styrene, dimethylstyrene, trimethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester, and 3-methyl.
• Styrene 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene,3-octyl Styrene, 4-octyl styrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allyl styrene, isopropenyl styrene, butenyl styrene, octenyl styrene, 4-t-butoxycarbonyl styrene, 4- Examples thereof include t-butoxystyrene and the like.
• Examples of the monofunctional vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexylmethyl vinyl ether and 4-methyl.
• Examples of the monofunctional N-vinyl compound include N-vinylcaprolactam, N-vinylpyrrolidone, N-vinyloxazolidinone, N-vinyl-5-methyloxazolidinone, and the like.
• the monofunctional monomer preferably contains at least one of a monofunctional (meth) acrylate and a monofunctional N-vinyl compound, and contains at least one of the monofunctional (meth) acrylate containing an alicyclic structure and the monofunctional N-vinyl compound. It is more preferable to include it.
• the monofunctional (meth) acrylate containing an alicyclic structure is preferably isobornyl (meth) acrylate, norbornyl (meth) acrylate, or adamantyl (meth) acrylate, and more preferably isobornyl (meth) acrylate.
• the total ratio of the monofunctional (meth) acrylate (preferably the monofunctional (meth) acrylate containing an alicyclic structure) and the monofunctional N-vinyl compound in the monofunctional monomer is 50% by mass to 100% by mass. It is more preferable, it is more preferably 60% by mass to 100% by mass, and further preferably 80% by mass to 100% by mass.
• the ratio of the monofunctional N-vinyl compound to the monofunctional monomer is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more.
• bifunctional monomer examples include a bifunctional (meth) acrylate, a bifunctional vinyl ether, a bifunctional monomer containing a vinyl ether group and a (meth) acryloyl group, and the like.
• bifunctional (meth) acrylate examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and dipropylene glycol di (meth).
• Examples of the bifunctional vinyl ether include 1,4-butanediol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, and hexanediol di.
• Examples thereof include vinyl ether, 1,4-cyclohexanedimethanol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F alkylene oxide divinyl ether.
• bifunctional monomer containing a vinyl ether group and a (meth) acryloyl group examples include 2- (2-vinyloxyethoxy) ethyl (meth) acrylate.
• trifunctional or higher functional monomer examples include trifunctional or higher functional (meth) acrylates, trifunctional or higher functional vinyl ethers, and the like.
• trifunctional or higher functional (meth) acrylate examples include trimethylol ethanetri (meth) acrylate, trimethylol propanetri (meth) acrylate, EO-modified trimethylol propanetri (meth) acrylate, and PO-modified trimethylol propanetri (meth) acrylate.
• trifunctional or higher functional vinyl ethers examples include trimethylol ethane trivinyl ether, trimethylol propanetrivinyl ether, ditrimethylol propanetetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, and EO.
• Trimethylol Propanetrivinyl Ether PO Modified Trimethylol Propanetrivinyl Ether, EO Modified Ditrimethylol Propanetetravinyl Ether, PO Modified Ditrimethylol Propanetetravinyl Ether, EO Modified Pentaerythritol Tetravinyl Ether, PO Modified Pentaerythritol Tetravinyl Ether, EO Modified Dipentaerythritol Hexavinyl ether, PO-modified dipentaerythritol hexavinyl ether, and the like can be mentioned.
• urethane (meth) acrylate examples include urethane (meth) acrylate.
• urethane (meth) acrylate examples include urethane (meth) acrylate, which is a reaction product of a bifunctional isocyanate compound and a hydroxyl group-containing (meth) acrylate.
• bifunctional isocyanate compound examples include Methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, octamethylene diisocyanate, 2,2 Alius diisocyanis such as 4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate; m-phenylenediocyanate, p-phenylenediocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diis
• Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxy.
• Examples thereof include butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, phenylglycidyl ether (meth) acrylate, pentaerythritol (meth) triacrylate, and dipentaerythritol penta (meth) acrylate.
• epoxy (meth) acrylate examples include epoxy (meth) acrylate.
• examples of the epoxy (meth) acrylate include a reaction product of (meth) acrylic acid and an epoxy resin.
• examples of the epoxy resin include bisphenol A type epoxy resin, cresol novolac type epoxy resin, and the like.
• the ink of the present disclosure contains at least one kind of inorganic oxide particles.
• the inorganic oxide particles include silica particles, alumina particles, titania particles, and the like.
• the inorganic oxide particles preferably contain at least one of silica particles and alumina particles, and more preferably contain silica particles, from the viewpoint of further improving the effect of suppressing the gloss of the image.
• the silica particles may be silica particles having a degree of hydrophobicity of less than 50 (that is, hydrophilic silica particles) or silica particles having a degree of hydrophobicity of 50 or more (that is, hydrophobic silica particles). ..
• the silica particles are preferably silica particles having a degree of hydrophobization of less than 50. The degree of hydrophobization of silica particles is measured by the following method.
• the ink is centrifuged to extract silica particles.
• 50 mL of ion-exchanged water and 0.2 g of extracted silica particles are placed in a beaker, and methanol is added dropwise from the burette to the beaker while stirring with a magnetic stirrer. As the methanol concentration in the beaker increases, the silica particles gradually settle. When the total amount of silica particles has subsided, the dropping of methanol is completed.
• the mass fraction (mass%) of methanol in the mixed solution of methanol and ion-exchanged water at the end of dropping methanol is defined as the degree of hydrophobicity.
• the degree of hydrophobicity of the silica particles is 60.
• the average primary particle size of the inorganic oxide particles is not particularly limited, but is preferably 0.1 ⁇ m to 3.0 ⁇ m.
• the average primary particle size of the inorganic oxide particles is 0.1 ⁇ m or more, the effect of suppressing the gloss of the image is more effectively exhibited.
• the average primary particle size of the inorganic oxide particles is 3.0 ⁇ m or less, it is advantageous in terms of ink ejection property. Further, when the average primary particle size of the inorganic oxide particles is 3.0 ⁇ m or less, as described above, it is difficult for the inorganic oxide particles alone to exhibit the function of the matting agent.
• the ink of the present disclosure contains an acid generator, as described above, the inorganic oxide particles aggregate on the surface side of the ink film to form an agglomerate, and this agglomerate functions as a matting agent. Demonstrate. As a result, the gloss of the image is suppressed.
• the average primary particle size of the inorganic oxide particles is more preferably 0.1 ⁇ m to 2.0 ⁇ m, further preferably 0.1 ⁇ m to 1.0 ⁇ m, and preferably 0.1 ⁇ m to 0.7 ⁇ m. More preferred.
• the average primary particle size of the inorganic oxide particles is a value measured using a transmission electron microscope (TEM).
• TEM transmission electron microscope
• a transmission electron microscope 1200EX manufactured by JEOL Ltd. can be used for the measurement. Specifically, from an image magnified 100,000 times by TEM after dropping 1,000-fold diluted ink onto a Cu200 mesh (manufactured by JEOL Ltd.) to which a carbon film is attached and drying it.
• the average primary particle size is obtained by measuring the equivalent circle diameter of 300 independent particles that do not overlap and averaging the measured values.
• the inorganic oxide particles may be used as the inorganic oxide particles.
• the inorganic oxide particles as a commercially available product of silica particles, for example, Seahoster KE-P30, Seahoster KE-P50, Seahoster KE-P100, Seahoster KE-P150, Seahoster KE-P250 (all manufactured by Nippon Shokubai Co., Ltd.), Aerosil series (manufactured by Evonik), QSG-100, QSG-170 (all manufactured by Shin-Etsu Chemical Co., Ltd.), And so on.
• examples of commercially available alumina particles include SMM-22 (manufactured by Nippon Light Metal Co., Ltd.) and the like.
• the content of the inorganic oxide particles with respect to the total amount of the ink is not particularly limited, but is preferably 0.2% by mass to 20.0% by mass, and is 0.5% by mass to 15.0% by mass. Is more preferable, 1.0% by mass to 10.0% by mass is further preferable, and 1.5% by mass to 8.0% by mass is further preferable.
• the content of the inorganic oxide particles is 0.2% by mass or more, the effect of suppressing the gloss of the image and the scratch resistance of the image are excellent.
• the content of the inorganic oxide particles is 20.0% by mass or less, the scratch resistance of the image and the ejection property of the ink are excellent.
• the ink of the present disclosure preferably contains at least one amine-based dispersant.
• the ink ejection property is further improved. It is considered that the reason why such an effect is obtained is that when the ink contains an amine-based dispersant, the dispersibility of the inorganic oxide particles in the ink is further improved.
• an amine-based resin dispersant is preferable.
• a commercially available product may be used as the amine-based dispersant.
• Commercially available products of amine-based dispersants include SOLSparse series (manufactured by Noveon) such as SOLSPERSE 13940, 17000, 20000, 24000, 26000, 28000, 32000, 35000, 36000, 39000.
• BYK Chemie such as 2163, 2164, 9076, 9077, DISPERBYK-9076
• BYKJET series such as BYKJET
• the content of the amine-based dispersant is preferably 20.0% by mass to 80.0% by mass, more preferably 30.0% by mass to 70.0% by mass, and 40.0% by mass, based on the total amount of the inorganic oxide particles. More preferably, it is by mass% to 70.0% by mass.
• the ink of the present disclosure contains at least one photoacid generator.
• the photoacid generator is not particularly limited as long as it is a substance that generates an acid when irradiated with light.
• Sulfonium salt or iodonium salt is preferred Sulfonium salts are more preferred
• a sulfonium salt containing at least one structure in which three aromatic rings are bonded to one S + is more preferable.
• the sulfonium salt as the photoacid generator is preferably a compound represented by any one of the following formulas (1) to (4).
• RS1 to RS17 each independently represent a hydrogen atom or a substituent.
• X - represents an anion.
• X - include anions represented by the halide ion (e.g., F -, Cl -, Br -, I - , etc.), B (C 6 F 5 ) 4 -, R 18 COO -, R 19 SO 3 - , SbF 6 -, AsF 6 - , PF 6 -, BF 4 - , and the like.
• R 18 and R 19 each independently represent an alkyl group which may have a substituent or a phenyl group which may have a substituent. Examples of the substituent of R 18 and R 19, include the substituents represented by R S1 ⁇ R S17, which will be described later.
• X - include anions represented by, B (C 6 F 5) 4 - or PF 6 - are preferable.
• R S1 ⁇ R S17 The substituent represented by R S1 ⁇ R S17, for example; Alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, decyl group and dodecyl group; Alkoxy groups having 1 to 12 carbon atoms such as methoxy group, ethoxy group, propyl group, butoxy group, hexyloxy group, decyloxy group and dodecyloxy group; Acyl groups having 1 to 13 carbon atoms such as formyl groups, acetyl groups, propionyl groups, decylcarbonyl groups, dodecylcarbonyl groups, and benzoyl groups; Acyloxy groups having 1 to 13 carbon atoms such as formyloxy group, acetoxy group, propionyl
• an iodonium salt containing at least one structure in which two aromatic rings are bonded to one I + is preferable.
• the iodonium salt is more preferably a compound represented by the following formula (I-1).
• R 1 and R 2 each independently represent a hydrogen atom or a substituent.
• X - represents an anion.
• iodonium salt a commercially available product may be used.
• a commercial product of iodonium salt for example; Omnicat 440 (manufactured by IGM Resins BV); Irgacure 250 (manufactured by BASF) (manufactured by BASF); And so on.
• a commercially available product of the photoacid generator or a commercially available product of the composition containing the photoacid generator may be used.
• Examples of a commercially available product of a photoacid generator or a commercially available product of a composition containing a photoacid generator include; CPI-100P, CPI-101A, CPI-110P, CPI-200K, CPI-210S, CPI-310B, CPI-410S, and IK-I (all manufactured by Sun Appro); Omnicat 250, Omnicat 270 (all manufactured by IGM Resins BV); Irgacure 290, Irgacure PAG103 (above, manufactured by BASF); TS-91, TS-01 (above, manufactured by Nippon Carbide Industry Co., Ltd.); And so on.
• the photoacid generator for example, the compounds described in paragraphs 0012 to 0017 and 0039 to 0048 of JP-A-2006-152064 can be used.
• the content of the photoacid generator with respect to the total amount of the ink is not particularly limited, but is preferably 0.1% by mass to 15.0% by mass, and 0.2% by mass to 15.0% by mass. Is more preferably 0.5% by mass to 10.0% by mass, further preferably 1.0% by mass to 9.0% by mass, and 1.5% by mass to 9.0% by mass. It is more preferably%.
• the content of the photoacid generator is 0.1% by mass or more, the effect of suppressing the gloss of the image is more excellent.
• the content of the photoacid generator is 15.0% by mass or less, the content of the radically polymerizable monomer can be increased, so that the image has better scratch resistance.
• the mass ratio of the content of the inorganic oxide particles to the content of the photoacid generator (hereinafter, also referred to as “(b) / (c)”) is not particularly limited, but the effect of suppressing the gloss of the image and the image From the viewpoint of being more excellent in abrasion resistance, it is preferably 0.1 to 80.0, more preferably 0.2 to 15.0, further preferably 0.5 to 10.0, and 0. It is more preferably .8 to 8.0.
• the content of each component is the content of the component with respect to the total amount of ink in units of mass%. It is a numerical value expressed and uses a numerical value with one digit after the decimal point. For example, when the content of the photoacid generator with respect to the total amount of ink is 1.5% by mass and the content of the inorganic oxide particles with respect to the total amount of ink is 2.0% by mass, "(b) / (c). ) ”,“ 1.5 ”is used as the content of the photoacid generator (corresponding to“ (c) ”), and the content of inorganic oxide particles (corresponding to“ (b) ”).
• the total content of the inorganic oxide particles and the photoacid generator (hereinafter, also referred to as “(b) + (c)”) with respect to the total amount of the ink is not particularly limited, but is 0.3% by mass to 25.0% by mass. %, More preferably 1.0% by mass to 17.5% by mass, further preferably 1.5% by mass to 10.0% by mass, and 2.0% by mass to 8%. It is more preferably 0.0% by mass.
• “(b) + (c)” is 0.3% by mass or more, it is excellent in the effect of suppressing the gloss of the image and the abrasion resistance of the image.
• “(b) + (c)” is 25.0% by mass or less, the effect of improving the scratch resistance of the image and the ink ejection property are excellent.
• the ink of the present disclosure preferably contains at least one photocation sensitizer.
• the photocation sensitizer can function as a sensitizer for photoacid generators. Therefore, when the ink of the present disclosure contains a photocation sensitizer, the action of the photoacid generator is further enhanced, and as a result, the effect of suppressing the gloss of the image is more excellent.
• a compound containing an anthracene skeleton is preferable.
• a compound containing an anthracene skeleton A compound in which an alkoxy group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) is bonded to both the 9-position and the 10-position of the anthracene skeleton, or 1 to 1 to 10 carbon atoms in both the 9-position and the 10-position of the anthracene skeleton.
• a compound having 20 (preferably 1 to 10 carbon atoms) conjugated with an acyloxy group is preferable. More preferred are 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, or 9,10-di (capryloyloxy) anthracene.
• anthracene UVS1331 manufactured by Kawasaki Kasei Chemicals Co., Ltd.
• Anthracene UVS1101 a commercial product of 9,10-diethoxyanthracene
• Anthracene UVS581 a commercially available product of 9,10-di (capryloyloxy) anthracene, And so on.
• the content of the photocation sensitizer with respect to the total amount of the ink is not particularly limited, but is preferably 0.2% by mass to 10.0% by mass, preferably 0.5% by mass to 5.0% by mass. More preferably, it is more preferably 0.5% by mass to 4.0% by mass.
• the content of the photocation sensitizer is 0.2% by mass or more, the action of the photoacid generator is further enhanced, and as a result, the effect of suppressing the gloss of the image is more excellent.
• the content of the photocation sensitizer is 10.0% by mass or less, the scratch resistance of the image is further improved.
• the ink of the present disclosure contains at least one photoradical polymerization initiator.
• a photoradical polymerization initiator Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-( 2-Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-benzyl-2- (dimethylamino) -4'-morpholinobtyrophenone, 2-methyl-1-[ 4- (Methylthio) phenyl] -2-morpholinopropan-1-one, etc.
• Alkylphenone-based photoradical polymerization initiator Benzoin-based photoradical polymerization initiators such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; Acylphosphine oxide-based photoradical polymerization initiators such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoindiphenylphosphine oxide; Benzyl glyoxy ester; Methylphenyl glyoxy ester; And so on. These specific examples are useful as small molecule photoradical polymerization initiators.
• the low molecular weight photoradical polymerization initiator means a photopolymerization initiator having a molecular weight of less than 500.
• the photoradical polymerization initiator may include a polymer photoradical polymerization initiator.
• the polymer photoradical polymerization initiator means a photopolymerization initiator having a molecular weight of 500 or more.
• the molecular weight of the polymer photoradical polymerization initiator is preferably 500 to 3000, more preferably 700 to 2500, and even more preferably 900 to 2100.
• known documents such as JP-A-2017-105902 (paragraph 0038, etc.) and JP-A-2017-522364 (paragraphs 0017-0053) can be referred to.
• a commercially available product may be used as the photoradical polymerization initiator.
• a commercial product for example IGM Resins B., a commercially available product of 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
• IGM Resins B. a commercially available product of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
• V. "Omnirad 819” made by the company, 2-Benzyl-2- (dimethylamino) -4'-morpholinoethanol on the market, IGM Resins B. et al. V.
• the content of the photoradical polymerization initiator with respect to the total amount of the ink is preferably 1.0% by mass to 20.0% by mass, more preferably 2.0% by mass to 15.0% by mass, and 3 It is more preferably 0.0% by mass to 10.0% by mass, and further preferably 3.0% by mass to 8.0% by mass.
• the content of the photoradical polymerization initiator is 1.0% by mass to 20.0% by mass, the scratch resistance of the image is further improved.
• the mass ratio of the content of the photoacid generator to the content of the photoradical polymerization initiator (hereinafter, also referred to as “(c) / (d)”) is excellent in the effect of suppressing the gloss of the image and the abrasion resistance of the image. From the viewpoint, it is preferably 0.01 to 2.50, preferably 0.02 to 2.50, more preferably 0.03 to 2.00, and 0.04 to 1.50. Is more preferable. “(C) / (d)” is calculated as a value having two digits after the decimal point.
• Mass ratio of total contents of radically polymerizable monomer, inorganic oxide particles, and photoacid generator to the content of photoradical polymerization initiator (hereinafter, "((a) + (b) + (c))) / (D) ”) is preferably 5.0 to 90.0, preferably 6.0 to 45.0, from the viewpoint of being excellent in the effect of suppressing the gloss of the image and the abrasion resistance of the image. It is more preferably 8.0 to 30.0, further preferably 8.0 to 20.0, and even more preferably 8.0 to 15.0. "((A) + (b) + (c)) / (d)” is calculated as a value having one digit after the decimal point.
• the ink of the present disclosure preferably contains at least one photoradical sensitizer from the viewpoint of further improving the scratch resistance of the image.
• Benzophenone o-benzoyl methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylicized benzophenone, 3,3', 4,4' -Benzophenone-based photoradical sensitizers such as tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone; Thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanth
• the photoradical sensitizer may include a polymeric photoradical sensitizer.
• the polymer photoradical sensitizer means a sensitizer having a molecular weight of 500 to 5000.
• the molecular weight of the polymer photoradical sensitizer is preferably 500 to 3000, more preferably 800 to 2500, and even more preferably 900 to 2100.
• the description in paragraphs 0035 to 0053 of JP-A-2014-162828 can be referred to.
• Examples of commercially available polymer photoradical sensitizers include; Speedcur (registered trademark) 7010 manufactured by Lambson (1,3-di ( ⁇ -[1-chloro-9-oxo-9H-thioxanthen-4-yl] oxy ⁇ acetylpoly [oxy (1-methylethylene)] oxy) -2,2-bis ( ⁇ - [1-chloro-9-oxo-9H-thioxanthen-4-yl] oxy ⁇ acetylpoly [oxy (1-methylethylene)] oxymethyl) propane, CAS No. 1003567-83-6 ); IGM Resins B. V.
• OMNIPOL® registered trademark
• TX Polybutyleneglycol bis (9-oxo-9H-thioxanthenyloxy) acetate, CAS No. 813452-37-8
• V. OMNIPOL BP Polybutyleneglycol bis (4-benzoylphenoxy) acetate, CAS No. 515136-48-8) RanA.
• the content of the photoradical sensitizer is preferably 0.1% by mass to 15% by mass, more preferably 0.% by mass, based on the total amount of the ink. It is 5% by mass to 10% by mass, more preferably 1% by mass to 5% by mass.
• the ink of the present disclosure may contain a gelling agent.
• a gelling agent that can be contained in the ink of the present disclosure, for example, known gelling agents described in paragraphs 0018 to 0032 of International Publication No. 2015/133605 can be applied.
• the gelling agent that can be contained in the ink of the present disclosure is preferably selected from the group consisting of an ester compound containing a chain alkyl group having 12 or more carbon atoms and a ketone compound containing a chain alkyl group having 12 or more carbon atoms. At least one species.
• an ester compound represented by the following formula (G1) is preferable.
• a ketone compound represented by the following formula (G2) is preferable.
• R 3- CO-R 4 ... Equation (G2) is preferable.
• R 1 to R 4 independently represent a chain alkyl group having 12 or more carbon atoms.
• the alkyl groups represented by R 1 to R 4 may contain a branched portion.
• the number of carbon atoms of the alkyl group represented by R 1 to R 4 is preferably 12 to 26.
• the melting point of the gelling agent is preferably 40 ° C. to 90 ° C., more preferably 50 ° C. to 80 ° C., and even more preferably 60 ° C. to 80 ° C.
• the content of the gelling agent is preferably 0.1% by mass to 5.0% by mass, more preferably 0.1% by mass, based on the total amount of the ink. % To 4.0% by mass, more preferably 0.5% by mass to 2.5% by mass.
• the ink of the present disclosure may or may not contain at least one colorant.
• the color material may be a visible color material or an invisible color material.
• the visible color material a color material having an absorbance in the wavelength range of 400 nm to 650 nm of more than 0.3 when a solution having a concentration of 0.01% by mass is prepared is preferable.
• the invisible color material is preferably a color material having an absorbance in the wavelength range of 400 nm to 650 nm of 0.3 or less when a solution having a concentration of 0.01% by mass is prepared.
• the invisible color material preferably has infrared absorption.
• having infrared absorbency means a substance having the highest absorbance of this solution at a wavelength of 650 nm to 1100 nm of 0.3 or more when a solution having a concentration of 0.01% by mass is prepared.
• the content of the coloring material is preferably 1% by mass to 20% by mass, and more preferably 2% by mass to 10% by mass, based on the total amount of the ink.
• the ink of the present disclosure is a clear ink for recording a clear image
• the ink of the present disclosure does not have to contain substantially a coloring material.
• the content of the coloring material may be less than 1% by mass, less than 0.1% by mass, or 0% by mass with respect to the total amount of the ink.
• the clear image means an image having a transmittance of 80% or more at a wavelength of 400 nm to 700 nm.
• the color material is not particularly limited, and can be arbitrarily selected and used from known color materials such as pigments and dyes. Among these, pigments are more preferable from the viewpoint of weather resistance.
• the pigment examples include resin particles dyed with a dye, a commercially available pigment dispersion or a surface-treated pigment [for example, a pigment dispersed in a dispersion medium (for example, a radical photopolymerizable monomer, an organic solvent, etc.), and The surface of the pigment is treated with a resin, a pigment derivative, etc.].
• examples of the pigment include visible pigments such as yellow pigment, red pigment, magenta pigment, blue pigment, cyan pigment, green pigment, orange pigment, purple pigment, brown pigment, black pigment and white pigment.
• examples of the pigment include an invisible pigment having infrared absorption.
• the ink of the present disclosure may further contain a pigment dispersant.
• a pigment dispersant paragraphs 0060 to 0074 of International Publication No. 2015/133605, paragraphs 0152 to 0158 of JP2011-225884A, paragraphs 0132 to 0149 of JP2009-209352, etc.
• Known documents can be referred to as appropriate.
• the invisible pigment having infrared absorption examples include an infrared absorbing pigment having a cyanine skeleton, a squarylium pigment, an infrared absorbing pigment having a phthalocyanine skeleton, and the like.
• the "cyanine skeleton” means a skeleton containing two nitrogen-containing heterocycles and a plurality of methine groups arranged between the two nitrogen-containing heterocycles.
• a squarylium pigment is particularly preferable.
• squarylium pigment As the squarylium pigment, a squarylium pigment having a volume average particle diameter of 10 nm to 400 nm is preferable.
• the volume average particle size of the squarylium pigment is preferably 15 nm or more, more preferably 20 nm or more, and even more preferably 50 nm or more. Further, when the average particle size of the squarylium pigment is 400 nm or less, the ink ejection property is ensured.
• the volume average particle size of the squarylium pigment is preferably 300 nm or less, more preferably 200 nm or less.
• the volume average particle size of the squarylium pigment can be measured by a dynamic light scattering method using a Nanotrack UPA particle size analyzer (trade name "UPA-EX150", manufactured by Nikkiso Co., Ltd.) as a measuring device.
• the measurement can be carried out according to a predetermined measurement method by placing 3 ml of the squarylium pigment dispersion in a measurement cell.
• the viscosity of the ink is used for the viscosity
• the density of the squarylium pigment is used for the density of the particles.
• the volume average particle size of the squarylium pigment can be adjusted by conditions such as the dispersion conditions of the squarylium pigment, specifically, the type of dispersant, the concentration of the squarylium pigment, and the combination of the radically polymerizable monomer and the dispersant.
• squarylium pigment a pigment of the squarylium pigment represented by the formula (SQ1) is preferable.
• rings A and B each independently represent an aromatic ring or a heteroaromatic ring
• X A and X B are each independently represent a monovalent substituent
• G A and G B Each independently represents a monovalent substituent
• kA represents an integer from 0 to nA
• kB represents an integer from 0 to nB.
• nA is G A represents the largest integer that can be substituted in the ring A
• nB represents the largest integer that can substituted can G B ring B.
• X A and G A, or X B and G B may each be bonded to each other to form a ring, if G A and G B are present in plural, the plurality of bonding to the ring A G A, And a plurality of GBs bonded to the ring B may be bonded to each other to form a ring structure.
• G A and G B represents a monovalent substituent independently.
• the monovalent substituent includes a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, -OR 10 , -COR 11 , -COOR 12 , and -OCOR.
• R 10 to R 27 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.
• R 12 of -COOR 12 is a hydrogen atom (that is, a carboxy group)
• the hydrogen atom may be dissociated (that is, a carbonate group) or may be in a salt state.
• R 24 of -SO 2 OR 24 is a hydrogen atom (that is, a sulfo group)
• the hydrogen atom may be dissociated (that is, a sulfonate group), or it may be in a salt state.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 8 carbon atoms.
• the alkyl group may be linear, branched, or cyclic, preferably linear or branched.
• the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
• the alkenyl group may be linear, branched, or cyclic, preferably linear or branched.
• the alkynyl group preferably has 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and particularly preferably 2 to 25 carbon atoms.
• the alkynyl group may be linear, branched, or cyclic, preferably linear or branched.
• the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
• the alkyl moiety of the aralkyl group is the same as the above alkyl group.
• the aryl moiety of the aralkyl group is the same as that of the above aryl group.
• the carbon number of the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and even more preferably 7 to 25.
• the heteroaryl group is preferably a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 8, and more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 4.
• the number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3.
• the hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
• the heteroaryl group is preferably a 5-membered ring or a 6-membered ring.
• the number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
• heteroaryl groups include pyridine ring, piperidine ring, furan ring group, furfuran ring, thiophene ring, pyrrole ring, quinoline ring, morpholine ring, indole ring, imidazole ring, pyrazole ring, carbazole ring, phenothiazine ring, phenoxazine.
• Examples thereof include a ring, an indole ring, a thiazole ring, a pyrazole ring, a thiadiazine ring, a benzoquinoline ring and a thiazizole ring.
• the alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group and heteroaryl group may have a substituent or may be unsubstituted.
• substituents include the substituents described in paragraph No. 0030 of JP-A-2018-154672.
• Preferred substituents include alkyl group, aryl group, amino group, alkoxy group, aryloxy group, aromatic heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group and alkoxycarbonylamino.
• Substituents of choice among which are alkyl groups, aryl groups, alkoxy groups, aryloxy groups, aromatic heterocyclic oxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, alkylthio groups, arylthios.
• a substituent selected from the group consisting of a group, an aromatic heterocyclic thio group, a sulfonyl group, a hydroxy group, a mercapto group, a halogen atom, a cyano group, a sulfo group, and a carboxy group is more preferable.
• the "carbon number" of the substituent means the "total carbon number" of the substituent. Further, for details of each substituent, reference can be made to the substituent described in paragraphs 0031 to 0035 of JP-A-2018-154672.
• X A and X B each independently represent a monovalent substituent.
• Substituents in X A and X B are preferably a group having an active hydrogen, -OH, -SH, -COOH, -SO 3 H, -NR X1 R X2, -NHCOR X1, -CONR X1 R X2, -NHCONR X1 R X2 , -NHCOOR X1 , -NHSO 2 R X1 , -B (OH) 2 or PO (OH) 2 are more preferred, and -OH, -SH or NR X1 R X 2 are even more preferred.
• RX1 and RX2 independently represent a hydrogen atom or a monovalent substituent.
• substituents examples include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heteroaryl group, and an alkyl group is preferable.
• the alkyl group is preferably linear or branched.
• Alkyl group, an alkenyl group, an alkynyl group, an aryl group and, for details of the heteroaryl group, is as defined and ranges described for the G A and G B.
• Ring A and ring B each independently represent an aromatic ring or a heteroaromatic ring.
• the aromatic ring and the heteroaromatic ring may be a monocyclic ring or a condensed ring.
• Specific examples of the aromatic ring and the heteroaromatic ring include a benzene ring, a naphthalene ring, a pentalene ring, an inden ring, an azulene ring, a heptalene ring, an indecene ring, a perylene ring, a pentacene ring, an acetaphthalene ring, a phenanthrene ring, an anthracene ring, and a naphthalene ring.
• X A and G A, X B and G B may be bonded to each other to form a ring, if G A and G B are present in plural may be bonded to each other to form a ring.
• a 5-membered ring or a 6-membered ring is preferable.
• the ring may be a single ring or a double ring.
• X A and G A, X B and G B when forming a G A s or G B are bonded to each other rings, may be they are attached directly to form a ring, an alkylene group, -CO-, Rings may be formed by bonding via a divalent linking group selected from the group consisting of -O-, -NH-, -BR- and combinations thereof.
• X A and G A, X B and G B, G A s or G B each other, it is preferable to form a ring via -BR-.
• R represents a hydrogen atom or a monovalent substituent.
• the substituent groups include the substituent described in the explanation of G A and G B, an alkyl group or an aryl group.
• kA represents an integer from 0 to nA
• kB represents an integer from 0 to nB
• nA represents the maximum integer substitutable for the A ring
• nB represents the maximum integer substitutable for the B ring.
• kA and kB 0 to 4 is preferable, 0 to 2 is more preferable, and 0 to 1 is particularly preferable, respectively. Further, it is preferable not to include the case where kA and kB simultaneously represent 0 (zero).
• the squarylium dye represented by the following formula (SQ2) is preferable in terms of resistance to light.
• R 1 and R 2 each independently represent a monovalent substituent
• R 3 and R 4 each independently represent a hydrogen atom or an alkyl group
• X 1 and X 2 independently represent an oxygen atom or -N (R 5 )-
• X 3 and X 4 independently represent a carbon atom or a boron atom, respectively.
• t represents 1 when X 3 is a boron atom and represents 2 when X 3 is a carbon atom.
• u represents 1 when X 4 is a boron atom and represents 2 when X 4 is a carbon atom.
• R 2 When X 4 is a carbon atom and u is 2, the two R 2s may be bonded to each other to form a ring.
• R 5 represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and Y 1 , Y 2 , Y 3 and Y 4 each independently represent a monovalent substituent, and Y 1 and Y 2 , And Y 3 and Y 4 may be bonded to each other to form a ring.
• Y 1 , Y 2 , Y 3 and Y 4 When a plurality of Y 1 , Y 2 , Y 3 and Y 4 are present, they may be combined with each other to form a ring.
• R 3 and R 4 each independently represent a hydrogen atom or an alkyl group.
• the alkyl group of R 3 has, for example, 1 to 4, preferably 1 or 2.
• the alkyl group may be linear or branched. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.
• R 3 is preferably a hydrogen atom, a methyl group, or an ethyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
• X 1 and X 2 independently represent an oxygen atom (-O-) or -N (R 5 )-.
• R 5 represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.
• R 5 is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.
• the alkyl group, aryl group and heteroaryl group represented by R 5 may be unsubstituted or have a monovalent substituent.
• the monovalent substituent include the monovalent substituent described in G A and G B described above.
• the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 4, and particularly preferably 1 to 2.
• the alkyl group may be either linear or branched.
• the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
• the heteroaryl group may be monocyclic or polycyclic.
• the number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3.
• the hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
• the number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
• the molecular weight of the squarylium dye represented by the above formula (SQ1) or formula (SQ2) is preferably in the range of 100 to 2,000, and more preferably in the range of 150 to 1,000.
• the squarylium dye represented by the formula (2) is described in detail in Japanese Patent Application Laid-Open No. 2011-2008101, and the compound described here can be suitably used as the squarylium dye in the present disclosure.
• the ink of the present disclosure may contain at least one polymerization inhibitor.
• Polymerization inhibitors include p-methoxyphenols, quinones (eg, hydroquinone, benzoquinone, methoxybenzoquinone, etc.), phenothiazines, catechols, alkylphenols (eg, dibutylhydroxytoluene (BHT), etc.), alkylbisphenols, dimethyldithiocarbamine.
• Zinc acid copper dimethyldithiocarbamate, copper dibutyldithiocarbamate, copper salicylate, thiodipropionic acid esters, mercaptobenzimidazole, phosphites, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), Examples thereof include 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl (TEMPOL) and tris (N-nitroso-N-phenylhydroxylamine) aluminum salt (also known as cuperon Al).
• TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl
• TMPOL 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl
• tris N-nitroso-N-phenylhydroxylamine aluminum salt
• At least one selected from p-methoxyphenols, catechols, quinones, alkylphenols, TEMPO, TEMPOL, and tris (N-nitroso-N-phenylhydroxylamine) aluminum salts is preferable, and p-methoxyphenols.
• Hydroquinone, benzoquinone, BHT, TEMPO, TEMPOL, and at least one selected from tris (N-nitroso-N-phenylhydroxylamine) aluminum salts are more preferred.
• the content of the polymerization inhibitor is preferably 0.01% by mass to 2.0% by mass and 0.02% by mass to 1.0 with respect to the total amount of the ink.
• mass% is more preferable, and 0.03% by mass to 0.5% by mass is particularly preferable.
• the ink of the present disclosure may contain a surfactant, but may contain substantially no surfactant.
• the content of the surfactant with respect to the total amount of the ink of the present disclosure may be 0.01% by mass or less, 0.0001% by mass or less, or 0% by mass. May be good.
• the ink of the present disclosure may contain a trace amount of an organic solvent as long as the above-mentioned effects are not impaired.
• the ink of the present disclosure preferably does not contain an organic solvent, or even if it contains an organic solvent, the content of the organic solvent is reduced.
• the content of the organic solvent with respect to the total amount of the ink is preferably less than 5% by mass, more preferably less than 3% by mass, and further preferably less than 1% by mass.
• the ink of the present disclosure may contain a trace amount of water as long as the above-mentioned effects are not impaired. However, from the viewpoint of more effectively obtaining the above-mentioned effects, it is preferable that the ink of the present disclosure does not contain water, or even if it contains water, the water content is reduced.
• the water content with respect to the total amount of the ink is preferably less than 5% by mass, more preferably less than 3% by mass, and even more preferably less than 1% by mass.
• the ink of the present disclosure may contain a cationically polymerizable monomer as long as the above-mentioned effects are not impaired.
• the cationically polymerizable monomer include compounds having an oxetane ring and epoxy compounds.
• JP-A-2006-152064 can be referred to.
• the ink of the present disclosure does not contain a cationically polymerizable monomer, or even if it contains a cationically polymerizable monomer, the content of the cationically polymerizable monomer is reduced.
• the content of the cationically polymerizable monomer with respect to the total amount of the ink is preferably less than 5% by mass, more preferably less than 3% by mass, still more preferably less than 1% by mass.
• the ink of the present disclosure may contain other components other than the above-mentioned components.
• other components include antibacterial agents, resins (for example, polyester resins, polyurethane resins, vinyl resins, acrylic resins, rubber resins, etc.).
• the ink of the present disclosure is preferably an inkjet ink.
• the surface tension of the ink of the present disclosure (that is, the surface tension at 25 ° C.) is preferably 20 mN / m to 50 mN / m, and more preferably 28 mN / m to 50 mN / m.
• the surface tension of the ink is 20 mN / m or more, the ejection property of the ink is further improved.
• the surface tension of the ink is 50 mN / m or less, the image quality of the image is further improved.
• the ink of the present disclosure preferably has a viscosity at 25 ° C. of 10 mPa ⁇ s to 50 mPa ⁇ s, more preferably 10 mPa ⁇ s to 30 mPa ⁇ s, and preferably 10 mPa ⁇ s to 25 mPa ⁇ s. More preferred.
• the viscosity of the ink can be adjusted, for example, by adjusting the composition ratio of each component contained.
• the viscosity referred to here is a value measured using a viscometer.
• VISCOMETER RE-85L manufactured by Toki Sangyo Co., Ltd.
• the viscosity of the ink is in the above-mentioned preferable range, the ejection stability can be further improved.
• the image recording method of the present disclosure is The step of applying the ink of the present disclosure described above on the recording medium to obtain an ink film (hereinafter, also referred to as “first application step”).
• the step of irradiating the ink film with active energy rays hereinafter, also referred to as "first irradiation step” and including.
• the image recording method of the present disclosure may include other steps, if necessary.
• the image recording method of the present disclosure uses the ink of the present disclosure. Therefore, according to the image recording method of the present disclosure, the same effect as that of the ink of the present disclosure is obtained.
• the recording medium in the image recording method of the present disclosure is not particularly limited.
• the recording medium include paper, paper on which plastic (for example, polyethylene, polypropylene, polystyrene, etc.) is laminated, a metal plate (for example, a metal plate such as aluminum, zinc, copper, etc.), and a plastic film (for example, poly).
• Vinyl chloride (PVC: Polyvinyl Chloride) resin cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate (PET), polypropylene (PE: Polyethylene), polystyrene ( PS: Polystyrene), polypropylene (PP: Polypropylene), polycarbonate (PC: Polycarbonate), polyvinyl acetal, acrylic resin and other films), paper on which the above-mentioned metals are laminated or vapor-deposited, and above-mentioned metals are laminated or vapor-deposited. Examples include plastic film.
• the ink of the present disclosure described above is applied onto the recording medium to obtain an ink film.
• the ink applying method include known methods such as a coating method, an inkjet method, and a dipping method.
• the inkjet method is preferable as the method of applying ink.
• the ink of the present disclosure is preferably an inkjet ink.
• the inkjet method has an advantage that a plate is not required and only a digital image can be dropped in a required amount at a required location.
• a known method of ejecting ink from a nozzle (ejection hole) of an inkjet head and applying the ink onto a recording medium can be applied, and the ink can be applied using an inkjet recording apparatus.
• the inkjet recording apparatus is not particularly limited, and a known inkjet recording apparatus capable of achieving the desired resolution can be arbitrarily selected and used. That is, a known inkjet recording device including a commercially available product can be used.
• Examples of the inkjet recording device include a device including an ink supply system, a temperature sensor, and a heating means.
• the ink supply system includes, for example, a source tank in which ink is stored, a supply pipe, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head.
• the piezo type inkjet head preferably has multi-size dots of 1 pL to 100 pL, more preferably 1 pL to 60 pL, preferably 320 dpi (dot per inch) ⁇ 320 dpi to 4000 dpi ⁇ 4000 dpi (dot per inch), more preferably 400 dpi ⁇ .
• dpi represents the number of dots per 2.54 cm (1 inch).
• the amount of droplets per drop ejected from each nozzle of the inkjet head is preferably 0.5 pL to 10 pL, although it depends on the resolution of the image, and in order to form a high-definition image, 0. It is more preferably 5 pL to 2.5 pL.
• the ink application method by the inkjet method may be either a single-pass method or a scanning method, but the single-pass method is preferable from the viewpoint of image recording speed. Further, in image recording in which an ink other than the ink of the present disclosure is applied by a single pass method, the gloss of the image tends to be remarkable. However, in the image recording using the ink of the present disclosure, the gloss of the image can be effectively suppressed even when the ink is applied by the single pass method.
• the single-pass method uses a line head in which nozzles are arranged corresponding to the entire area of one side of the recording medium as an inkjet head, the line heads are fixedly arranged, and the recording medium is a line head.
• the scanning method is a method in which a short serial head is used as the inkjet head and ink is applied to the recording medium by scanning the short serial head.
• the transport speed of the recording medium is preferably 1 m / s to 120 m / s, more preferably 50 m / s to 120 m / min.
• the preferable range of the transport speed of the recorded medium in the second and subsequent steps is the same as the preferable range of the transport speed of the recorded medium in the first step.
• the transport speed of the recorded medium may be the same throughout all the steps, or the transport speed of the recorded medium may be changed in at least a part of the steps.
• First irradiation step the ink film obtained in the first application step is irradiated with active energy rays.
• the ink film is irradiated with active energy rays to polymerize at least a part of the radically polymerizable monomers in the ink film to obtain an image.
• the active energy ray is compared with the case where substantially all of the radically polymerizable monomer in the ink film is polymerized. Reduce the irradiation energy of.
• polymerizing only a part of the radically polymerizable monomer in the ink film is also referred to as “temporary curing", and irradiation of active energy rays for temporary curing is also referred to as “pinning exposure”.
• polymerizing substantially all of the radically polymerizable monomers in the ink film is also referred to as “main curing”, and irradiation with active energy rays for main curing is also referred to as "main exposure”.
• the first irradiation step is It may be a step of applying pinning exposure (that is, temporary curing) to the ink film, or It may be a step of subjecting the ink film to main exposure (that is, main curing). It may be a step of applying the pinning exposure and the main exposure to the ink film in this order.
• pinning exposure that is, temporary curing
• main exposure that is, main curing
• the first irradiation step is a step of applying pinning exposure (that is, temporary curing) to the ink film
• an image of the temporarily cured ink film is obtained by the first irradiation step.
• the first irradiation step is a step of applying main exposure (that is, main curing) to the ink film, or a step of applying pinning exposure and main exposure to the ink film in this order
• the first irradiation step is performed. An image that is the main cured ink film can be obtained.
• the image recording method preferably further includes a second applying step and a second irradiation step described later.
• the reaction rate of the ink film after pinning exposure is preferably 10% to 80%.
• the reaction rate of the ink film means the polymerization rate of the radically polymerizable monomer in the ink film obtained by high performance liquid chromatography.
• the reaction rate of the ink film is 10% or more, insufficient spread of dots of the ink (for example, the second ink described later) applied on the ink film is suppressed, and as a result, the image finally obtained is obtained.
• the graininess of for example, a multi-order color image described later
• is improved that is, the graininess of the image is reduced).
• reaction rate of the ink film is 80% or less, excessive spread of the ink (for example, the second ink described later) applied on the ink film is suppressed, and the ink dots are suppressed. Drip interference between each other is suppressed, and as a result, the image quality of the finally obtained image is improved.
• the reaction rate of the ink film is preferably 15% or more from the viewpoint of further improving the graininess of the finally obtained image.
• the reaction rate of the ink film is preferably 75% or less, more preferably 50% or less, and preferably 40% or less, from the viewpoint of further improving the image quality of the finally obtained image. It is more preferably 30% or less, and further preferably 25% or less.
• the reaction rate of the ink film after the main exposure is preferably more than 80% and 100% or less, more preferably 85% to 100%, still more preferably 90% to 100%.
• the reaction rate is more than 80%, the adhesion of the image is further improved.
• the reaction rate of the ink film is determined by the following method. Prepare a recording medium that has been operated until the end of irradiation of the ink film on the recording medium with active energy rays, and prepare a sample piece having a size of 20 mm ⁇ 50 mm from the region where the ink film of the recording medium exists. (Hereinafter referred to as a sample piece after irradiation) is cut out, and the cut out sample piece after irradiation is immersed in 10 mL of THF (tetrahydrofuran) for 24 hours to obtain an eluate in which ink is eluted.
• THF tetrahydrofuran
• the amount of radically polymerizable monomer (hereinafter referred to as “amount of monomer after irradiation X1”) is determined by high performance liquid chromatography. Separately, the same operation as above is performed except that the ink film on the recording medium is not irradiated with active energy rays, and the amount of radically polymerizable monomer (hereinafter referred to as “non-irradiated monomer amount X1”) is determined.
• the active energy ray in the irradiation step is preferably UV light (that is, ultraviolet light), and more preferably 385 nm to 410 nm. UV light having the highest illuminance in the wavelength range.
• the UV light source that is, the light source of UV light
• a known UV light source in which at least one of the illuminance and the irradiation time is variable can be used.
• the UV light source is preferably an LED (Light Emitting Diode) light source.
• Irradiation of the active energy rays in the irradiation step may be performed in an environment where the oxygen concentration is 20% by volume or less (more preferably less than 20% by volume, still more preferably 5% by volume or less).
• the environment in which the oxygen concentration is less than 20% by volume is preferably in the presence of an inert gas (for example, nitrogen gas, argon gas, helium gas).
• the illuminance of the active energy ray for the pinning exposure is preferably 0.10 W / cm to 0.50 W / cm, more preferably 0.20 W / cm, from the viewpoint of more easily achieving the reaction rate of the above-mentioned ink. It is ⁇ 0.49 W / cm, more preferably 0.20 W / cm to 0.45 W / cm.
• the irradiation energy of the active energy ray for pinning exposure (hereinafter, also referred to as “exposure amount”) is preferably 2 mJ / cm 2 to 20 mJ / cm 2 from the viewpoint of more easily achieving the above-mentioned reaction rate of the ink. , More preferably 4 mJ / cm 2 to 15 mJ / cm 2 .
• the illuminance of the active energy ray for the main exposure is preferably 1.0 W / cm or more, more preferably 2.0 W / cm or more, from the viewpoint of further improving the adhesion between the recording medium and the image. More preferably, it is 4.0 W / cm or more.
• the upper limit of the illuminance of the active energy ray for the main exposure is not particularly limited, but the upper limit is, for example, 10 W / cm.
• the irradiation energy (that is, the amount of exposure) of the active energy ray for the main exposure is preferably 20 mJ / cm 2 or more, more preferably 80 mJ / cm, from the viewpoint of further improving the adhesion between the recording medium and the image. It is cm 2 or more.
• the upper limit of the irradiation energy of the active energy ray for the main exposure is not particularly limited, but the upper limit is, for example, 240 mJ / cm 2 .
• a second ink is applied onto an ink film (hereinafter, also referred to as "first ink film”) irradiated with active energy rays in the first irradiation step, and the first ink film is coated with the second ink. It may include a second application step of obtaining a second ink film in contact with the ink film.
• the second ink is preferably an active energy ray-curable ink containing a radically polymerizable monomer and a photopolymerization initiator, and more preferably the ink of the present disclosure.
• the second ink applied in the second application step may be only one type or two or more types. It is preferable that the ink of the present disclosure (hereinafter, also referred to as the first ink) applied in the first application step and the second ink have different hues. When the hues of the first ink and the second ink are different, images of multiple colors (for example, secondary colors) can be recorded.
• the second ink may be applied over the first ink film and the first ink film non-forming region. Further, in the second application step, the second ink may be applied on at least a part of the first ink film, and does not necessarily have to be applied on the entire first ink film.
• the method of applying the second ink is the same as the method of applying the first ink, and the preferred embodiment is also the same.
• the image recording method of the present disclosure of the aspect including the second addition step it is possible to record a multi-order color image in which gloss is suppressed.
• the image recording method of the present disclosure of the aspect including the second application step may further include a second irradiation step of irradiating the entire first ink film and the second ink film with the second active energy ray. ..
• the second irradiation step is It may be a step of applying pinning exposure (that is, temporary curing) to the entire first ink film and the second ink film. It may be a step of subjecting the entire first ink film and the second ink film to main exposure (that is, main curing). It may be a step of applying the pinning exposure and the main exposure to the entire first ink film and the second ink film in this order.
• pinning exposure that is, temporary curing
• main exposure that is, main curing
• main exposure that is, main curing
• the preferred embodiment of the second active energy ray and its irradiation conditions is the same as the preferred embodiment of the active energy ray and its irradiation conditions in the first irradiation step.
• the preferable irradiation conditions of the pinning exposure and the main exposure in the second irradiation step are the same as the preferable irradiation conditions of the pinning exposure and the main exposure in the first irradiation step.
• Magenta pigment mill base (hereinafter, also referred to as "M pigment mill base”) and squarylium pigment mill base (hereinafter, also referred to as “SQ pigment mill base”) were prepared as pigment dispersions used for ink preparation. Specifically, each component in the composition of each pigment mill base is placed in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 8 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm. , Each pigment mill base was obtained.
• M50 manufactured by Eiger
• -M pigment mill-based composition- -M pigment magenta pigment; CINQUASIA MAGENTA RT-355D (manufactured by BASF Japan): 30 parts by mass-SR9003 (manufactured by Sartmer; propoxylation as PO-modified neopentyl glycol diacrylate (2) neopentyl glycol diacrylate) : 50 parts by mass ⁇ SOLPERSE 32000 (manufactured by Lubrizol; amine-based dispersant): 20 parts by mass
• -SQ pigment mill-based composition- -SQ pigment (squarylium pigment; pigment of specific example B-1 of the above-mentioned squarylium pigment: 30 parts by mass-SR9003 (manufactured by Sartmer; propoxylation as PO-modified neopentyl glycol diacrylate (2) neopentyl glycol diacrylate) : 50 parts by mass ⁇ SOLPERSE 35000 (manufactured by Lubrizol; amine-based dispersant): 20 parts by mass
• An image recording device (specifically, an inkjet recording device) including a UV light source, a yellow ink head, a UV light source, a white ink head, and a nitrogen purge UV exposure machine was prepared.
• the transport system was a single-pass type sheet-fed printing press.
• the black ink head, the cyan ink head, the magenta ink head, and the yellow ink head are each piezo-type inkjet heads (specifically, line heads) equipped with inkjet nozzles (hereinafter, also simply referred to as “nozzles”). ). From each nozzle, 1 pL to 60 pL multi-size dots can be ejected at a resolution of 1,200 ⁇ 1,200 dpi. Here, dpi represents the number of dots per 2.54 cm.
• the ink supply system of this inkjet recording device is composed of a main tank, a supply pipe, an ink supply tank immediately before the inkjet head, a filter, and an inkjet head.
• the portion of the ink supply system from the ink supply tank to the inkjet head was heat-insulated and heated. Further, temperature sensors were provided near the nozzles of the ink supply tank and the inkjet head, respectively, and the temperature was controlled so that the nozzle portion was always 70 ° C. ⁇ 2 ° C. However, only in the examples using the ink containing the gelling agent, the temperature was controlled so that the nozzle portion was always 90 ° C. ⁇ 2 ° C.
• the original tank connected to the magenta ink head contained one of the inks for each embodiment and the inks for each comparative example.
• an LED (Light Emitting Diode) lamp (Co., Ltd.) capable of irradiating UV light having the maximum illuminance in the wavelength range of 385 nm to 410 nm, respectively. Kyocera 4 cm width, G4B, maximum illuminance 10 W) was used.
• Each of these UV light sources is a UV light source whose illuminance and irradiation time of UV light can be changed.
• the recording medium is so that the irradiation of UV light to the landed ink is started 0.1 seconds after the ink ejected from each head lands on the recording medium. The transport speed was adjusted.
• Examples 1 to 41, Comparative Examples 1 to 3 Using each ink, image recording device, and recording medium (OK top coated paper (84.9 g / m 2 , manufactured by Oji Paper Co., Ltd.)), various images were recorded based on the above image recording method, and each evaluation was performed. carried out.
• ink is applied to the recording medium in a solid shape so that the halftone dot area ratio is 100%, and the applied ink has an illuminance of 0.40 W / cm 2.
• An image (specifically, a solid image) is obtained by irradiating UV light for 0.024 seconds (pinning exposure) and then irradiating UV light for 0.024 seconds (main exposure) with an illuminance of 5.0 W / cm 2.
• the pinning exposure was carried out in an atmosphere (oxygen concentration 20%) by a UV light source immediately after the magenta ink head.
• the main exposure was carried out by a nitrogen purge UV exposure machine in an atmosphere having an oxygen concentration of 1% and a nitrogen concentration of 99%.
• the gloss difference [image-recording medium] was less than 20.
• the gloss difference [image-recording medium] was 20 or more and less than 25.
• the gloss difference [image-recording medium] was 25 or more and less than 30.
• the gloss difference [image-recording medium] was 30 or more and less than 40.
• the gloss difference [image-recording medium] was 40 or more.
• ⁇ Abrasion resistance of images> A 150 g paperweight was placed on the image, and in this state, the rubbing operation of reciprocating the paperweight on the image was repeatedly performed. The rubbing operation for one round trip of the paperweight was set to one rubbing operation, and when each of the following rubbing operations was completed, it was confirmed whether or not the image was scratched. Based on the confirmed results, the scratch resistance of the image was evaluated according to the following evaluation criteria. In the following evaluation criteria, the rank with the best scratch resistance of the image is "5". However, for the comparative example, this evaluation was omitted, and "-" was described in the column of abrasion resistance in Table 1.
• ⁇ Ink ejection property> The ink was continuously ejected from the magenta ink head of the image recording device for 5 minutes in a mode of 1,200 dpi, and an evaluation was carried out to confirm the number of nozzle omissions in this operation. The above evaluation was carried out 6 times, and based on the obtained results, the ink ejection property was evaluated according to the following evaluation criteria. In the following evaluation criteria, the rank with the best ink ejection property is "5". However, for the comparative example, this evaluation was omitted, and "-" was described in the discharge property column of Table 1.
• NVC N-vinyl caprolactam
• IBOA Isobornyl acrylate.
• TMPTA Trimethylolpropane triacrylate.
• SR454 ... SR454 manufactured by Sartmer.
• SR9003 ... SR9003 manufactured by Sartmer.
• TPO IGM Resins B. V. "Omnirad TPO” manufactured by the company. 2,4,6-trimethylbenzoyldiphenylphosphine oxide. 819 ... IGM Resins B. V. "Omnirad 819” manufactured by the company. Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
• ITX 2-Isopropylthioxanthone.
• S7010 Speedcure 7010 manufactured by Rambson (polymer photoradical sensitizer. The compound name is as described above).
• UV-12 ... "FLORSTAB UV12” manufactured by Kromachem. Nitroso-based polymerization inhibitor. Tris (N-nitroso-N-phenylhydroxylamine) aluminum salt.
• KE-P50 ... “Seahoster KE-P50” manufactured by Nippon Shokubai Co., Ltd. (silica particles, average primary particle size 0.5 ⁇ m).
• KE-P100 ... “Seahoster KE-P100” manufactured by Nippon Shokubai Co., Ltd. (silica particles, average primary particle size 1.0 ⁇ m).
• KE-P150 ... “Seahoster KE-P150” manufactured by Nippon Shokubai Co., Ltd. (silica particles, average primary particle size 1.5 ⁇ m).
• KE-P250 “Seahoster KE-P250” manufactured by Nippon Shokubai Co., Ltd. (silica particles, average primary particle size 2.5 ⁇ m).
• QSG-170 ... "QSG-170” manufactured by Shin-Etsu Chemical Co., Ltd. (silica particles, average primary particle size 0.17 ⁇ m).
• SMM-22 “SMM-22” manufactured by Nippon Light Metal Co., Ltd. (alumina particles, average primary particle size 0.5 ⁇ m).
• SOLSPERSE 32000 ... "SOLSPERSE 32000” manufactured by Lubrizol.
• DISPERBYK-108 ... "DISPERBYK-108” manufactured by BYK Chemie.
• DISPERBYK-2008 ...
• Example 12 in which the photoacid generator was a sulfonium salt was superior due to the effect of suppressing the gloss of the image.
• Examples 36 to 38 in Examples 36 and 37 in which the content of the photocation sensitizer was 5.0% by mass or less with respect to the total amount of the ink, the scratch resistance of the image was excellent.
• Examples 15 to 21 in Examples 16 to 21, in which the content of the inorganic oxide particles is 0.5% by mass or more with respect to the total amount of the ink, the effect of suppressing the gloss of the image and the scratch resistance of the image are obtained.
• Examples 16 to 22 in Examples 16 to 21, in which the content of the inorganic oxide particles is 15.0% by mass or less with respect to the total amount of the ink, the ink ejection property and the image abrasion resistance are excellent.
• Example 16 to 22 in Examples 16 to 21, in which the content of the inorganic oxide particles is 15.0% by mass or less with respect to the total amount of the ink, the ink ejection property and the image abrasion resistance are excellent.
• Example 24 in which the mass ratio of the content of the inorganic oxide particles to the content of the photoacid generator (“(b) / (c)”) is 0.2 to 15.0. From 29 to 29, it was excellent in the effect of suppressing the gloss of the image and the abrasion resistance of the image.
• Examples 16 to 21 in which the total content of the inorganic oxide particles and the photoacid generator (“(b) + (c)”) with respect to the total amount of the ink is 1.0% by mass or more. It was excellent in the effect of suppressing the gloss of the image and the scratch resistance of the image.
• Example 31 to 34 the mass ratio of the total contents of the radically polymerizable monomer, the inorganic oxide particles, and the photoacid generator to the content of the photoradical polymerization initiator (“((a) + (b)).
• + (c)) / (d) was 6.0 to 45.0, the effect of suppressing the gloss of the image and the scratch resistance of the image were excellent.
• the radically polymerizable monomer contains at least one of a monofunctional monomer and a bifunctional monomer, and the total content of the monofunctional monomer and the bifunctional monomer is 50% by mass or more based on the total amount of the ink.
• the ink ejection property and the scratch resistance of the image were excellent.
• examples of the inks of the present disclosure include magenta inks and squarylium pigment inks as invisible inks, but inks of colors other than magenta, invisible inks other than squarylium pigment inks, and clear inks are used. Needless to say, even when the ink is used, the same effect as that of the above-mentioned Examples can be obtained as long as the conditions of the ink of the present disclosure are satisfied.
• an ink film of the first color is formed and subjected to pinning exposure, and then the radical polymerizable monomer and a photopolymerization initiator are overlapped with at least a part of the ink film of the first color.
• the second and subsequent color inks containing the colorant are applied to form the second and subsequent color ink films, and then the first color ink film and the second and subsequent color ink films are subjected to main exposure to obtain a multicolor image.

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• 2021
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