WO2023181502A1 - Procédé d'impression d'image - Google Patents

Procédé d'impression d'image Download PDF

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Publication number
WO2023181502A1
WO2023181502A1 PCT/JP2022/043642 JP2022043642W WO2023181502A1 WO 2023181502 A1 WO2023181502 A1 WO 2023181502A1 JP 2022043642 W JP2022043642 W JP 2022043642W WO 2023181502 A1 WO2023181502 A1 WO 2023181502A1
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Prior art keywords
ink
light source
recording method
mass
wavelength
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PCT/JP2022/043642
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English (en)
Japanese (ja)
Inventor
俊之 幕田
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富士フイルム株式会社
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Publication of WO2023181502A1 publication Critical patent/WO2023181502A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

  • the present disclosure relates to an image recording method.
  • an image recording method As a type of image recording method, an image recording method is known in which an image is obtained by applying ink onto a substrate and curing the ink by irradiating the applied ink with active energy rays such as ultraviolet rays. .
  • active energy rays such as ultraviolet rays.
  • consideration has been given to replacing ultraviolet rays with electron beams as active energy rays used for irradiation.
  • Japanese Patent Laid-Open No. 2009-83267 discloses a process of applying an undercoat liquid onto a recording medium, a process of forming an image by discharging a colored liquid onto the undercoat liquid, and a process of curing the colored liquid.
  • a UV light source and an electron beam irradiation device are described as means for curing.
  • JP 2018-86726A discloses a composition application step of applying a curable composition containing a polymerizable compound onto a recording medium, and an irradiation step of irradiating the curable composition with two or more types of active energy rays.
  • At least an electron beam with an accelerating voltage of 130 kV or less is used as the active energy ray in the irradiation step, and the electron beam is irradiated with an absorbed dose of 20 to 75 kGy in the irradiation step.
  • the method is described.
  • the present disclosure has been made in view of the above circumstances, and an embodiment of the present invention provides an image recording method that can suppress migration and record an image that has excellent adhesion to a base material. be done.
  • the present disclosure includes the following aspects. ⁇ 1> Apply a first ink containing a polymerizable compound and a first hydrogen abstraction type polymerization initiator having a molecular weight of 500 or more and having a maximum absorption wavelength on the longest wavelength side of 350 nm or less on a base material. a step of exposing the base material to which the first ink has been applied using a first light source having an emission maximum wavelength in a wavelength range of 350 nm or less; On the applied area, a second ink containing a polymerizable compound and a second hydrogen abstraction type polymerization initiator having a molecular weight of 500 or more and having a maximum absorption wavelength in a wavelength range exceeding 350 nm is applied using an inkjet recording method.
  • An image recording method comprising the step of, after exposure, irradiating an electron beam onto a base material to which a first ink and a second ink have been applied.
  • the first ink and the second ink are each The image recording method according to any one of ⁇ 1> to ⁇ 4>, further comprising an amine having a molecular weight of 500 or more.
  • the first ink is a clear ink with a colorant content of 0.1% by mass or less based on the total amount of the first ink, or a white ink containing a white pigment, ⁇ 1> to ⁇ 5 >The image recording method according to any one of >.
  • ⁇ 7> The image recording method according to any one of ⁇ 1> to ⁇ 6>, wherein in the step of applying the first ink, the first ink is applied by an inkjet recording method.
  • an image recording method in which migration is suppressed and an image can be recorded with excellent adhesion to a base material.
  • a numerical range expressed using " ⁇ " means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
  • the amount of each component in the composition means the total amount of the multiple substances present in the composition. do.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step, Further, the values may be replaced with the values shown in the examples.
  • the term "step” is included not only in an independent step but also in the case where the intended purpose of the step is achieved even if the step cannot be clearly distinguished from other steps.
  • (meth)acrylate is a concept that includes both acrylate and methacrylate
  • (meth)acryloyl group is a concept that includes both acryloyl group and methacryloyl group
  • (meth)acrylate is a concept that includes both acryloyl group and methacryloyl group
  • “Acrylic acid” is a concept that includes both acrylic acid and methacrylic acid.
  • image refers to any film formed using ink
  • image recording refers to the formation of an image (that is, a film).
  • image in this disclosure also includes a solid image.
  • the image recording method includes, on a base material, a polymerizable compound and a first hydrogen abstraction type polymerization initiator having a molecular weight of 500 or more and a maximum absorption wavelength on the longest wavelength side of 350 nm or less. a step of exposing the substrate to which the first ink has been applied using a first light source having an emission maximum wavelength in a wavelength range of 350 nm or less; and exposure by the first light source.
  • a second hydrogen-abstracting polymerization initiator containing a polymerizable compound and a second hydrogen-abstracting polymerization initiator having a molecular weight of 500 or more and having a maximum absorption wavelength in a wavelength range exceeding 350 nm is applied onto the area to which the first ink has been applied.
  • the image recording method it is possible to record an image in which migration is suppressed and which has excellent adhesion to the base material.
  • migration refers to a phenomenon in which components in an image are eluted from an image recorded with ink
  • amount of migration refers to the amount of components (including polymerizable compounds and polymerization initiators) eluted due to migration. means.
  • the emission maximum is in the wavelength region of 350 nm or less.
  • a first light source having a wavelength polymerization of the polymerizable compound contained in the first ink progresses, and a first ink film is formed.
  • the amount of the polymerizable compound decreases due to polymerization, it is considered that some of the polymerizable compound remains in the first ink film (not completely disappeared).
  • the second ink contains a second hydrogen abstraction type polymerization initiator having an absorption maximum wavelength in a wavelength region exceeding 350 nm
  • a second light source having an emission maximum wavelength of over 350 nm on the shortest wavelength side can be used.
  • polymerization of the polymerizable compound contained in the second ink proceeds, and a second ink film is formed on the first ink film.
  • the first ink contains a first hydrogen abstraction polymerization initiator whose maximum absorption wavelength on the longest wavelength side is 350 nm or less, the first ink has a maximum emission wavelength of more than 350 nm on the shortest wavelength side.
  • the progress of polymerization of the polymerizable compound contained in the first ink film is suppressed. Therefore, it is considered that it is possible to make a state in which a portion of the polymerizable compound remains in the first ink film before irradiation with the electron beam.
  • radicals are generated in the base material, and the radicals generated in the base material react with the polymerizable compound in the first ink film, resulting in a covalent bond between the base material and the first ink film. It is presumed that the adhesion between the material and the image is improved.
  • the base material to which the first ink has been applied is exposed using a first light source, and the base material to which the first ink and the second ink have been applied is exposed to light using a second light source.
  • radically active species are generated while the polymerizable compound remains in the first ink film and the second ink film, and in the state in which the radically active species are generated, an electron beam is applied. It is presumed that the irradiation accelerates the polymerization reaction and suppresses migration.
  • JP-A No. 2009-83267 and JP-A No. 2018-86726 do not include any description regarding a multi-stage exposure process.
  • the image recording method includes, on a base material, a polymerizable compound and a first hydrogen abstraction type polymerization initiator having a molecular weight of 500 or more and a maximum absorption wavelength on the longest wavelength side of 350 nm or less. (hereinafter also referred to as "first ink applying step").
  • the base material is not particularly limited, and any known base material can be used.
  • the base material include paper base materials, paper base materials laminated with resin (e.g., polyethylene, polypropylene, polystyrene, etc.), resin base materials, and metal plates (e.g., metal plates such as aluminum, zinc, copper, etc.). , a paper base material on which the above-mentioned metal is laminated or vapor-deposited, a resin base material on which the above-mentioned metal is laminated or vapor-deposited, and the like.
  • resin e.g., polyethylene, polypropylene, polystyrene, etc.
  • metal plates e.g., metal plates such as aluminum, zinc, copper, etc.
  • the base material examples include textile base materials.
  • Textile base materials include natural fibers such as cotton, silk, hemp, and wool; chemical fibers such as viscose rayon and rheocell; synthetic fibers such as polyester, polyamide, and acrylic; natural fibers, chemical fibers, and synthetic fibers.
  • the base material may be a permeable base material or a non-permeable base material, but is preferably a non-permeable base material.
  • the non-permeable base material is defined by the water absorption rate (mass%, 24hr. ) is less than 0.2.
  • the impermeable base material is not particularly limited, and examples thereof include thermoplastic resin base materials.
  • resin base materials include base materials made of thermoplastic resin molded into various shapes such as three-dimensional shapes such as bottles, sheet shapes, film shapes, etc.
  • the resin in the resin base material includes at least one selected from the group consisting of polyester (e.g., polyethylene terephthalate, polyethylene naphthalate, etc.), polypropylene, polyethylene, polyvinyl chloride, nylon, polyimide, polycarbonate, and polystyrene. is preferred.
  • the resin base material may be surface-treated from the viewpoint of improving surface energy.
  • Surface treatments include, but are not limited to, corona treatment, plasma treatment, flame treatment, heat treatment, abrasion treatment, light irradiation treatment (UV treatment), flame treatment, and the like.
  • a resin beverage container for example, a plastic bottle
  • a resin food packaging material is preferable.
  • the first ink contains at least one polymerizable compound. Due to the exposure, the polymerizable compound in the first ink is polymerized, the first ink is cured, and an image is formed.
  • the polymerizable group contained in the polymerizable compound may be a cationically polymerizable group or a radically polymerizable group, but from the viewpoint of curability, it is preferably a radically polymerizable group.
  • the radically polymerizable group is preferably an ethylenically unsaturated group from the viewpoint of curability.
  • 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 molecular weight of the polymerizable compound is preferably 1000 or less, more preferably 800 or less, from the viewpoint of ejection properties.
  • the lower limit of the molecular weight of the polymerizable compound is, for example, 58 (molecular weight of methyl vinyl ether).
  • the first ink preferably contains a polymerizable monomer as a polymerizable compound.
  • the molecular weight of a compound having a molecular weight of 1000 or less can be calculated based on the type and number of atoms constituting the compound.
  • the polymerizable monomer may be a monofunctional polymerizable monomer containing one polymerizable group, or may be a polyfunctional polymerizable monomer containing two or more polymerizable groups.
  • the monofunctional polymerizable monomer is not particularly limited as long as it is a compound containing one polymerizable group. From the viewpoint of curability, the monofunctional polymerizable monomer is preferably a monofunctional radically polymerizable monomer, and more preferably a monofunctional ethylenically unsaturated monomer.
  • monofunctional ethylenically unsaturated monomers include monofunctional (meth)acrylates, monofunctional (meth)acrylamides, monofunctional aromatic vinyl compounds, monofunctional vinyl ethers, and monofunctional N-vinyl compounds.
  • the polyfunctional polymerizable monomer is not particularly limited as long as it is a monomer containing two or more polymerizable groups. From the viewpoint of curability, the polyfunctional polymerizable monomer is preferably a polyfunctional radically polymerizable monomer, and more preferably a polyfunctional ethylenically unsaturated monomer. Examples of the polyfunctional ethylenically unsaturated monomer include polyfunctional (meth)acrylate compounds and polyfunctional vinyl ethers.
  • polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and propylene glycol di(meth)acrylate.
  • polyfunctional vinyl ether examples 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 hexane divinyl ether.
  • the polymerizable monomer in the first ink preferably contains a polyfunctional polymerizable monomer from the viewpoint of further improving image adhesion and further suppressing migration.
  • the proportion of the polyfunctional polymerizable monomer in the total amount of polymerizable monomers contained in the first ink is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more.
  • the proportion of the polyfunctional polymerizable monomer may be 100% by mass.
  • Polyfunctional polymerizable monomers include bifunctional polymerizable monomers (i.e. compounds containing two polymerizable groups) and trifunctional polymerizable monomers (i.e. It is preferable that at least one of the compounds containing three polymerizable groups is included.
  • the total proportion of bifunctional polymerizable monomers and trifunctional polymerizable monomers in the total amount of polymerizable monomers contained in the first ink is preferably 30% by mass or more, and 50% by mass or more. More preferably, it is 60% by mass or more.
  • the total proportion of the bifunctional polymerizable monomer and the trifunctional polymerizable monomer may be 100% by mass.
  • the polyfunctional polymerizable monomer it is more preferable to include a bifunctional polymerizable monomer from the viewpoint of reducing the viscosity of the first ink and improving the ejection properties.
  • the proportion of the bifunctional polymerizable monomer in the total amount of polymerizable monomers contained in the ink is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more. preferable.
  • the content of the polymerizable compound is preferably 50% by mass or more, more preferably 60% by mass or more, and 80% by mass or more based on the total amount of the first ink. is even more preferable.
  • the upper limit of the content of the polymerizable compound is, for example, 99% by mass.
  • the first ink contains at least one first hydrogen abstraction type polymerization initiator having a molecular weight of 500 or more and a maximum absorption wavelength on the longest wavelength side of 350 nm or less.
  • a hydrogen abstraction type polymerization initiator having a molecular weight of 500 or more and an absorption maximum wavelength on the longest wavelength side of 350 nm or less is also simply referred to as a "first hydrogen abstraction type polymerization initiator.”
  • the first hydrogen abstraction type polymerization initiator has a molecular weight of 500 or more, image migration is suppressed.
  • the upper limit of the molecular weight of the first hydrogen abstraction type polymerization initiator is not particularly limited, and is, for example, 5,000.
  • the first hydrogen abstraction type polymerization initiator has a maximum absorption wavelength on the longest wavelength side of 350 nm or less. That is, the first hydrogen abstraction type polymerization initiator does not have an absorption peak in a wavelength region exceeding 350 nm.
  • the absorption maximum wavelength of a polymerization initiator means the wavelength at which the absorbance is maximum in the absorption spectrum of light incident on a polymerization initiator-containing solution with a concentration of 0.005% by mass.
  • the absorption maximum wavelength is a value measured using an ultraviolet-visible near-infrared spectrophotometer.
  • a spectrophotometer for example, the V-770 series manufactured by JASCO Corporation can be used.
  • the first ink is temporarily cured in the first exposure step described below, and the curing does not proceed in the second exposure step described later. Therefore, in the first hydrogen abstraction type polymerization initiator, the maximum value of absorbance in the wavelength region exceeding 350 nm is preferably 0.2 or less with respect to the maximum value of absorbance in the wavelength region of 350 nm or less. More preferably, it is 1 or less.
  • the first hydrogen abstraction type polymerization initiator is preferably a benzophenone compound.
  • Examples of the first hydrogen abstraction type polymerization initiator include polybutylene glycol (4-benzoylphenoxy) acetate, anthraquinone, and acetophenone.
  • the first hydrogen abstraction type polymerization initiator examples include, for example, Omnipol BP (manufactured by IGM Resins, molecular weight 730) and Genopol BP-2 (manufactured by Rahn, molecular weight 980).
  • the content of the first hydrogen abstraction type polymerization initiator is preferably 0.5% to 10% by mass, and 1% to 5% by mass, based on the total amount of the first ink. It is more preferable that it is mass %.
  • the first ink may contain components other than the polymerizable compound and the first hydrogen abstraction type polymerization initiator.
  • the first ink contains at least one amine having a molecular weight of 500 or more.
  • the amine having a molecular weight of 500 or more together with the first hydrogen abstraction type polymerization initiator, the polymerization reaction is promoted and migration is further suppressed.
  • the amine having a molecular weight of 500 or more may be a compound containing an amino group (that is, containing at least one of an unsubstituted amino group and a substituted amino group) and a molecular weight of 500 or more, and is not particularly limited in other respects.
  • Examples of the amine having a molecular weight of 500 or more include a compound represented by the following formula (X).
  • R 1 , R 2 , and R 3 each independently represent a hydrogen atom or a substituent. However, R 1 , R 2 , and R 3 are selected such that the molecular weight of the compound represented by formula (X) is 500 or more. ]
  • R 1 , R 2 , and R 3 are preferably substituents, and all three of R 1 , R 2 , and R 3 are preferably substituents. More preferred.
  • the substituent include a (meth)acryloyloxy group, a phenyl group, and an aliphatic group (eg, an alkyl group).
  • R 1 , R 2 , and R 3 contain a (meth)acryloyloxy group.
  • the amine with a molecular weight of 500 or more contains at least one amino group, but from the viewpoint of viscosity and migration suppression, the amine with a molecular weight of 500 or more preferably contains 1 to 6 amino groups, and 1 to 3 amino groups. It is more preferable to contain 1 or 2 amino groups, and even more preferably to contain 1 or 2 amino groups.
  • the amine with a molecular weight of 500 or more contains a (meth)acryloyloxy group
  • the amine with a molecular weight of 500 or more preferably contains 1 to 6 (meth)acryloyl groups, It is more preferable to contain 1 to 4 (meth)acryloyl groups, and even more preferable to contain 1 or 2 (meth)acryloyl groups.
  • Examples of amines having a molecular weight of 500 or more include aminoethylated acrylic polymers, poly-2-(dimethylamino)ethyl acrylate, and ⁇ -[4-dimethylamino)-benzoyl]- ⁇ -[[4-(dimethylamino)]. -benzoyl]-oxy]-poly-(oxy-1,2-ethanediyl).
  • the amine having a molecular weight of 500 or more commercially available products may be used.
  • amines with a molecular weight of 500 or more include, for example; GENOMER5161, GENOMER5271, GENOMER5275, GENOMER5795 (all manufactured by Rahn); CN371, CN373, CN383, CN384, CN386, CN501, CN550, CN551 (all manufactured by Sartomer); EBECRYL7100, EBECRYL80, EBECRYL81, EBECRYL83, EBECRYL84, EBECRYLP115 (all manufactured by Daicel Cytec); Laromer PO77F (LR8946), Laromer LR8956, Laromer LR8996, Laromer PO94F (LR8894) (manufactured by BASF); Photomer4771, Photomer4775, Photomer4967, Photomer5006, Photomer5096, Photomer5662, Photomer5930 (all manufactured by Cognis); DoublecureEPD, DoublecureOPD, Doublecure115, Double-Co
  • the molecular weight of the amine having a molecular weight of 500 or more is preferably 700 or more, more preferably 800 or more, and even more preferably 1000 or more, from the viewpoint of further suppressing migration.
  • the upper limit of the molecular weight of the amine having a molecular weight of 500 or more is preferably 10,000, more preferably 7,000, and still more preferably 5,000.
  • the content of the amine having a molecular weight of 500 or more is preferably 0.5% by mass to 10% by mass, and 1% by mass to 5% by mass, based on the total amount of the first ink, from the viewpoint of ink viscosity and image quality. It is more preferable that
  • the first ink may contain at least one colorant.
  • the colorant may be either a pigment or a dye. From the viewpoint of durability, the colorant is preferably a pigment.
  • the pigment may be either an organic pigment or an inorganic pigment that is normally commercially available.
  • pigments include “Dictionary of Pigments” edited by Seishiro Ito (published in 2000), W. Herbst, K.
  • Examples include pigments described in “Industrial Organic Pigments” by Hunger, JP 2002-12607, JP 2002-188025, JP 2003-26978, and JP 2003-342503.
  • the first ink is a clear ink with a colorant content of 0.1% by mass or less based on the total amount of the first ink, or a white ink containing a white pigment. It is preferable that
  • the content of the colorant is 0.05% by mass or less based on the total amount of the first ink, and it does not contain a colorant (that is, the content of the colorant is 0.05% by mass or less). % by mass) is more preferable.
  • the content of the white pigment is preferably 5% to 25% by mass, and preferably 8% to 20% by mass, based on the total amount of the first ink. More preferred.
  • the first ink contains a pigment
  • a pigment dispersant is a compound that has the function of dispersing pigments.
  • the pigment can be dispersed in the first ink by adsorbing the pigment dispersant onto the surface of the pigment and covering at least a portion of the surface of the pigment.
  • the form of the pigment dispersant contained in the first ink is not particularly limited, and may be any one of a random polymer, a block polymer, and a graft polymer. Further, the pigment dispersant may be a polymer having a crosslinked structure.
  • a polymer refers to a compound having a weight average molecular weight of 1000 or more.
  • weight average molecular weight means a value measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • HLC registered trademark
  • 8020GPC manufactured by Tosoh Corporation
  • TSKgel registered trademark
  • Super Multipore HZ-H 4 mm ID x 15 cm
  • the measurement is performed using an RI detector with a sample concentration of 0.45% by mass, a flow rate of 0.35 ml/min, a sample injection amount of 10 ⁇ l, and a measurement temperature of 40° C.
  • the calibration curve is "standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: "F-40", “F-20”, “F-4", “F-1”, "A-5000”, "A- 2500'', ⁇ A-1000'', and 8 samples of ⁇ n-propylbenzene''.
  • the pigment dispersant may be a commercially available product.
  • Commercially available products include, for example, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-110, DISPERBYK-111, DISPERBYK-161, DISPERBYK-162, DISPERBYK -163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK- 168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-182 (manufactured by BYK Chemie); and SOLSPERSE3000, SOLSPERSE5000, SOLSPERSE9000, SOLSPER SE12000, SOLSPERSE13240, SOLSPERSE13940, SOLSPERSE17000, SOLSPERSE22000, SOLSPERSE24000, SOLSPER
  • the content of the pigment dispersant relative to the content of the pigment is preferably 0.05 to 1.0, and preferably 0.1 to 0.5, on a mass basis from the viewpoint of dispersion stability. It is more preferable.
  • the first ink may contain other components other than the above components, if necessary.
  • other components include surfactants, sensitizers, co-sensitizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antifading agents, conductive salts, organic solvents, and basic compounds. It will be done.
  • the viscosity of the first ink is preferably 0.5 mPa ⁇ s to 30 mPa ⁇ s, more preferably 2 mPa ⁇ s to 20 mPa ⁇ s, preferably 2 mPa ⁇ s to 15 mPa ⁇ s, and 3 mPa ⁇ s. - It is more preferable that it is s to 10 mPa ⁇ s.
  • the viscosity is measured at 25° C. using a viscometer, for example, a TV-22 viscometer manufactured by Toki Sangyo Co., Ltd.
  • the surface tension of the first ink is preferably 60 mN/m or less, more preferably 20 mN/m to 50 mN/m, and even more preferably 25 mN/m to 45 mN/m.
  • the surface tension is measured at 25° C. using a surface tension meter, for example, by the plate method using an automatic surface tension meter (product name “CBVP-Z”) manufactured by Kyowa Interface Science.
  • the method for applying the first ink is not particularly limited, and known methods such as a coating method, an inkjet recording method, and a dipping method can be used. Among these, the first ink is preferably applied using an inkjet recording method.
  • the inkjet recording method is not particularly limited as long as it can record an image, and any known method can be used.
  • Inkjet recording methods include, for example, a charge control method that uses electrostatic attraction to eject ink, a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element, and a method that converts electrical signals into acoustic beams to eject ink.
  • the acoustic inkjet method uses radiation pressure to eject ink by irradiating the ink with water, and the thermal inkjet method (bubble jet (registered trademark)) uses the pressure generated by heating the ink to form bubbles. .
  • the inkjet heads used in the inkjet recording method include the shuttle method, which uses a short serial head and performs recording while scanning the head in the width direction of the substrate, and the shuttle method, in which recording elements are arranged to cover the entire side of the substrate.
  • the shuttle method which uses a short serial head and performs recording while scanning the head in the width direction of the substrate
  • the shuttle method in which recording elements are arranged to cover the entire side of the substrate.
  • One example is the line method using a line head.
  • a pattern can be formed on the entire surface of the substrate by scanning the substrate in a direction that intersects with the direction in which the recording elements are arranged, eliminating the need for a conveyance system such as a carriage that scans the short head.
  • the line method eliminates the need for complicated scanning control between carriage movement and the base material, and only the base material moves, making it possible to achieve higher recording speeds than with the shuttle method.
  • the amount of droplets of the first ink ejected from the inkjet head is preferably 1 pL (picoliter) to 100 pL, more preferably 3 pL to 80 pL, and even more preferably 3 pL to 50 pL.
  • the first ink may be applied to at least a portion of the base material.
  • the first ink is preferably an ink for forming a base layer, and in this case, it is preferably applied to the entire surface of the base material.
  • the image recording method includes a step of exposing a substrate to which a first ink has been applied using a first light source having a maximum emission wavelength in a wavelength range of 350 nm or less (hereinafter referred to as "first exposure step"). ).
  • the first ink applied in the first ink application step contains a first hydrogen abstraction type polymerization initiator whose absorption maximum wavelength on the longest wavelength side is 350 nm or less, and in the first exposure step, the first ink is applied in the wavelength region of 350 nm or less. Since exposure is performed using the first light source having the maximum emission wavelength, polymerization of the polymerizable compound contained in the first ink can proceed.
  • the exposure in the first exposure step is suitable as pinning exposure, and the exposure in the first exposure step allows the first ink to be temporarily cured.
  • Temporal curing refers to polymerizing only a part of the polymerizable compound in the ink.
  • the first exposure step it is preferable to polymerize only a part of the polymerizable compound in the first ink. That is, it is preferable that a part of the polymerizable compound contained in the first ink remains in the first ink film formed by the first ink at the end of the first exposure step. If some of the polymerizable compound remains in the first ink film, radicals generated on the base material when irradiated with an electron beam in the electron beam irradiation step described below will cause the polymerizable compound in the first ink film to As a result, the base material and the first ink film are covalently bonded, and the adhesion between the base material and the image is improved.
  • the second ink applied on the first ink film is prevented from penetrating into the first ink film, and the obtained The optical density of the image is improved.
  • the first light source is not particularly limited as long as it has a maximum emission wavelength in a wavelength range of 350 nm or less, and may have a maximum emission wavelength in a wavelength range exceeding 350 nm.
  • the maximum emission wavelength of a light source means the wavelength at which the emission intensity is maximum in the emission spectrum of the light source.
  • the first light source a known light source for ultraviolet irradiation (UV light source) in which at least one of illuminance and irradiation time is variable can be used.
  • the UV light source include semiconductor light sources such as an LED (Light Emitting Diode) light source, an LD (Laser Diode) light source, and an SLD (Superluminescent diode) light source.
  • LED Light Emitting Diode
  • LD Laser Diode
  • SLD Superluminescent diode
  • the UV light source is an LED light source.
  • the amount of exposure from the first light source is preferably 2 mJ/cm 2 to 20 mJ/cm 2 , more preferably 4 mJ/cm 2 to 15 mJ/cm 2 .
  • the image recording method includes, after the first exposure step, a polymerizable compound having a molecular weight of 500 or more and having a maximum absorption wavelength in a wavelength range exceeding 350 nm, on the area to which the first ink is applied.
  • the method includes a step of applying a second ink containing a first hydrogen abstraction type polymerization initiator using an inkjet recording method (hereinafter also referred to as a "second ink applying step").
  • the second ink contains at least one polymerizable compound. Due to the exposure, the polymerizable compound in the second ink is polymerized, the second ink is cured, and an image is formed.
  • the preferred embodiments of the polymerizable compound contained in the second ink are the same as the preferred embodiments of the polymerizable compound contained in the first ink.
  • the second ink contains at least one second hydrogen abstraction type polymerization initiator that has a molecular weight of 500 or more and has a maximum absorption wavelength in a wavelength region exceeding 350 nm.
  • a hydrogen abstraction type polymerization initiator having a molecular weight of 500 or more and having a maximum absorption wavelength in a wavelength region exceeding 350 nm is also simply referred to as a "second hydrogen abstraction type polymerization initiator.”
  • the second hydrogen abstraction type polymerization initiator has a molecular weight of 500 or more, image migration is suppressed.
  • the upper limit of the molecular weight of the second hydrogen abstraction type polymerization initiator is not particularly limited, and is, for example, 5,000.
  • the second hydrogen abstraction type polymerization initiator only needs to have a maximum absorption wavelength in a wavelength region exceeding 350 nm, and may have a maximum absorption wavelength in a wavelength region of 350 nm or less.
  • the absorption maximum wavelength is a value measured using an ultraviolet-visible near-infrared spectrophotometer.
  • a spectrophotometer for example, the V-770 series manufactured by JASCO Corporation can be used.
  • the second hydrogen abstraction type polymerization initiator is preferably a thioxanthone compound.
  • Preferred thioxanthone compounds include compounds represented by the following formula (S1).
  • R 1 and R 2 each independently represent an alkyl group having 1 to 5 carbon atoms or a halogen atom
  • x represents an integer of 2 to 4
  • j represents an integer of 0 to 4.
  • k represents an integer from 0 to 3
  • X 1 represents an x-valent linking group containing at least one of a hydrocarbon chain, an ether bond, and an ester bond.
  • the compound represented by formula (S1) may be a commercially available product.
  • Commercially available products include, for example, 1,3-di( ⁇ -[1-chloro-9-oxo-9H-thioxanthen-4-yl)oxy]acetylpoly[oxy(1-methylethylene)] ⁇ oxy) -2,2-bis( ⁇ -[1-methylethylene)] ⁇ oxymethyl)propane (product name: Speedcure 7010, manufactured by Lambson), polybutylene glycol bis(9-oxo-9H-thioxanthenyloxy)acetate (product name "OMNIPOL TX", manufactured by IGM Resins B.V.), and product name "GENOPOL TX-2", manufactured by Rahn).
  • Second hydrogen abstraction type polymerization initiators examples include Speedcure 7010 (manufactured by Lambson, molecular weight 1899).
  • the content of the second hydrogen abstraction type polymerization initiator is preferably 0.5% to 10% by mass, and 1% to 5% by mass based on the total amount of the second ink. % is more preferable.
  • the second ink may contain components other than the polymerizable compound and the first hydrogen abstraction type polymerization initiator.
  • the second ink preferably contains at least one amine having a molecular weight of 500 or more.
  • Preferred embodiments of the amine with a molecular weight of 500 or more that can be included in the second ink are the same as the preferred embodiments of the amine with a molecular weight of 500 or more that can be included in the first ink.
  • the content of the amine having a molecular weight of 500 or more is preferably 0.5% by mass to 10% by mass, and 1% by mass to 5% by mass, based on the total amount of the first ink, from the viewpoint of ink viscosity and image quality. It is more preferable that
  • the second ink contains at least one colorant.
  • the colorant may be either a pigment or a dye. From the viewpoint of durability, the colorant is preferably a pigment. Details of the pigment are as described above.
  • the colorant contained in the second ink When the first ink is a clear ink, the colorant contained in the second ink must be a colorant that exhibits an achromatic color such as white or black, or a colorant that exhibits a chromatic color such as cyan, magenta, or yellow. is preferred.
  • the colorant contained in the second ink is preferably a colorant with a hue other than white, and specifically, a colorant exhibiting black, cyan, magenta, It is preferable that the coloring agent exhibits a chromatic color such as yellow. That is, the second ink is preferably a color ink.
  • the content of the white pigment is preferably 5% to 25% by mass, and preferably 8% to 20% by mass, based on the total amount of the second ink. More preferred.
  • the content of the pigment other than the white pigment is preferably 1% by mass to 15% by mass, and 2% by mass to 10% by mass, based on the total amount of the second ink. It is more preferable that it is mass %.
  • a color image (character image, line image, pattern image, etc.) with high optical density is placed on the white base layer. images can be recorded.
  • the second ink contains a pigment
  • the preferred embodiments of the pigment dispersant that may be included in the second ink are the same as the preferred embodiments of the pigment dispersant that may be included in the first ink.
  • the second ink may contain other components other than the above components, if necessary.
  • examples of other components include surfactants, sensitizers, co-sensitizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antifading agents, conductive salts, organic solvents, and basic compounds. It will be done.
  • the second ink is applied using an inkjet recording method. Details of the inkjet recording method are as described above.
  • the second ink may be applied to at least a portion of the area to which the first ink has been applied.
  • the first ink is applied to a part of the substrate, if the second ink is applied to the area to which the first ink was applied, the second ink is applied to an area other than the area to which the first ink was applied. It may be given.
  • the image recording method according to the present disclosure includes a step (hereinafter referred to as , also referred to as "second exposure step").
  • the first ink applied in the first ink application step contains a first hydrogen abstraction type polymerization initiator whose maximum absorption wavelength on the longest wavelength side is 350 nm or less.
  • the second ink applied in the second ink applying step includes a second hydrogen abstraction type polymerization initiator having a maximum absorption wavelength in a wavelength region exceeding 350 nm.
  • the second exposure step since exposure is performed using a second light source whose emission maximum wavelength on the shortest wavelength side exceeds 350 nm, the polymerization of the polymerizable compound contained in the first ink film is suppressed, and the second ink film is The polymerization of the polymerizable compound contained in the polymerizable compound can proceed.
  • the second exposure step polymerization of the polymerizable compound contained in the first ink film is suppressed, and a part of the polymerizable compound can remain in the first ink film.
  • the radicals generated on the base material react with the polymerizable compound in the first ink film, and the base material and the first ink film form a covalent bond. This improves the adhesion between the base material and the image.
  • the exposure in the second exposure step is suitable as pinning exposure, and the second ink can be temporarily cured by the exposure in the second exposure step.
  • the second exposure step it is preferable to polymerize only a portion of the polymerizable compound in the second ink. That is, at the end of the second exposure step, it is preferable that a part of the polymerizable compound contained in the second ink remains in the second ink film formed by the second ink. If a portion of the polymerizable compound remains in the second ink film, migration will be further suppressed when electron beam irradiation is performed in the electron beam irradiation step described below. This is thought to be because radically active species are generated in the second ink film in the second exposure step, and the polymerization reaction is promoted by irradiating the electron beam while the radically active species are generated. It will be done.
  • the second light source is a light source whose maximum emission wavelength on the shortest wavelength side is over 350 nm. That is, the second light source does not have an emission peak in a wavelength region of 350 nm or less.
  • the first ink is temporarily cured in the first exposure step and that curing does not proceed in the second exposure step. Therefore, in the second light source, the maximum value of the emission intensity in the wavelength region of 350 nm or less is preferably 0.2 or less, and 0.1 or less with respect to the maximum value of the emission intensity in the wavelength region of more than 350 nm. It is more preferable that there be.
  • the second light source may be a light source provided with a cut filter that blocks light emission in the wavelength region of 350 nm or less.
  • UV light source a known light source for ultraviolet irradiation (UV light source) in which at least one of illuminance and irradiation time is variable can be used.
  • the UV light source include semiconductor light sources such as LED light sources, LD light sources, and SLD light sources.
  • the UV light source is an LED light source.
  • At least one of the first light source and the second light source is preferably an LED light source, and more preferably the first light source and the second light source are LED light sources.
  • the amount of exposure from the second light source is preferably 2 mJ/cm 2 to 20 mJ/cm 2 , more preferably 4 mJ/cm 2 to 15 mJ/cm 2 .
  • the image recording method according to the present disclosure includes a step (hereinafter referred to as (also referred to as “electron beam irradiation process").
  • the polymerization of the polymerizable compound contained in the first ink and the polymerizable compound contained in the second ink is advanced. be able to.
  • the first ink and the second ink are cured and an image is recorded on the substrate.
  • Irradiation with an electron beam can be performed using an electron beam irradiation device.
  • the electron beam irradiation conditions are not particularly limited.
  • the acceleration voltage for electron beam irradiation is, for example, 50 kV to 200 kV, preferably 50 kV to 110 kV.
  • the dose in electron beam irradiation is, for example, 10 kGy to 100 kGy, preferably 30 kGy to 90 kGy.
  • the processing speed for electron beam irradiation is, for example, 1 m/min to 200 m/min.
  • the electron beam irradiation 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). This suppresses polymerization inhibition caused by oxygen and further suppresses migration.
  • the environment where the oxygen concentration is less than 20% by volume is preferably in the presence of an inert gas (for example, nitrogen gas, argon gas, and helium gas).
  • an inert gas for example, nitrogen gas, argon gas, and helium gas.
  • the image recording method according to the present disclosure may include steps other than those described above, as necessary.
  • the area to which the first ink and the second ink have been applied A step of applying a third ink onto the substrate using an inkjet recording method (hereinafter also referred to as "third ink applying step"), and a substrate to which the first ink, second ink, and third ink are applied, A step of exposing using a third light source whose emission maximum wavelength on the shortest wavelength side exceeds 350 nm (hereinafter referred to as "third exposure step”) is performed, and then the first ink, the second ink, and You may carry out the process of irradiating an electron beam with respect to the base material provided with the 3rd ink.
  • the first ink is preferably a clear ink with a colorant content of 0.1% by mass or less based on the total amount of the first ink, and the second ink contains a white pigment.
  • the third ink is a color ink containing a colorant of a hue other than white.
  • the third light source has a maximum emission wavelength on the shortest wavelength side of more than 350 nm. Therefore, the polymerization of the polymerizable compound contained in the first ink film can be suppressed, and the polymerization of the polymerizable compounds contained in the second ink and the third ink can proceed.
  • the third exposure step polymerization of the polymerizable compound contained in the first ink film is suppressed, and a part of the polymerizable compound can remain in the first ink film.
  • the radicals generated on the base material react with the polymerizable compound in the first ink film, and the base material and the first ink film form a covalent bond. This improves the adhesion between the base material and the image.
  • a preferred embodiment of the third light source is the same as a preferred embodiment of the second light source.
  • a cyan pigment dispersion and a white pigment dispersion were prepared in advance.
  • Cyan pigment dispersion D1C was obtained by putting each of the components shown below into a dispersion machine Motor Mill M50 (manufactured by Eiger) and dispersing using zirconia beads with a diameter of 0.65 mm at a circumferential speed of 9 m/s for 4 hours. Obtained.
  • White pigment dispersion D1W was also prepared in the same manner.
  • Cyan ink C2 In the composition of cyan ink C1, 6% by mass of 3-methyl-1,5-pentanediol diacrylate was changed to 3% by mass of second hydrogen abstraction type polymerization initiator A and 3% by mass of amine A. Cyan ink C2 was prepared in the same manner as cyan ink C1 except for the above.
  • ⁇ Second hydrogen abstraction type polymerization initiator A Product name "Speedcure 7010", manufactured by Lambson, molecular weight 1899, maximum absorption wavelength in a wavelength region exceeding 350 nm.
  • ⁇ Amine A Product name "Genomer 5271", manufactured by Rahn, molecular weight 2300)
  • White ink W2 In the composition of white ink W1, 6% by mass of 3-methyl-1,5-pentanediol diacrylate was changed to 3% by mass of secondary hydrogen abstraction type polymerization initiator A and 3% by mass of amine A. White ink W2 was prepared in the same manner as white ink W1 except for the above.
  • White ink W3 In the composition of white ink W1, 6% by mass of 3-methyl-1,5-pentanediol diacrylate was changed to 3% by mass of first hydrogen abstraction type polymerization initiator A and 3% by mass of amine A. White ink W3 was prepared in the same manner as white ink W1 except for the above.
  • First hydrogen abstraction type polymerization initiator A Product name "Omnipol BP", manufactured by IGM Resins, molecular weight 730, absorption maximum wavelength 340 nm on the longest wavelength side
  • White ink W4 In the composition of white ink W1, 6% by mass of 3-methyl-1,5-pentanediol diacrylate was changed to 3% by mass of first hydrogen abstraction type polymerization initiator B and 3% by mass of amine B. White ink W4 was prepared in the same manner as white ink W1 except for the above.
  • Amine B Product name “Omnipol ASA”, manufactured by IGM Resins, molecular weight 510
  • the following single-pass inkjet recording device was prepared as an image recording device.
  • the single-pass inkjet recording device has a single-pass inkjet head (specifically, a Samba (registered trademark) head manufactured by Fujifilm Dymatex, 1200 npi, minimum liquid appropriate amount) installed on the table conveyance system along the conveyance path. Three 2pL (hereinafter also simply referred to as "heads") were arranged. Clear ink was introduced into the most upstream head, white ink was introduced into the middle head, and cyan ink was introduced into the most downstream head.
  • a replaceable light source was placed directly downstream of each head. Further downstream of the light source placed immediately downstream of the cyan ink head, an electron beam (EB) irradiation device Eye Compact EB (manufactured by Eye Electron Beam Co., Ltd.) was placed.
  • EB electron beam
  • a substrate (product name "LL-RP2", manufactured by Futamura Chemical Co., Ltd., thickness 50 ⁇ m) that had been subjected to corona treatment immediately before image recording was set on a conveyance table.
  • the base material was transported at a transport speed of 50 m/min, each ink was applied to the base material being transported, a 100% solid image was recorded, and an image recording material was obtained.
  • Examples 1-1, 1-2 and Comparative Examples 1-1 to 1-6 white ink was used as the first ink, cyan ink was used as the second ink, and the first ink and second ink listed in Table 1 were used. The inks were sequentially applied and exposed under the exposure conditions listed in Table 1.
  • Examples 2-1, 2-2 and Comparative Examples 2-1 to 2-8 clear ink was used as the first ink, white ink was used as the second ink, and cyan ink was used as the third ink. The first ink, the second ink, and the third ink were applied in this order and exposed under the exposure conditions listed in Table 2.
  • Tables 1 and 2 "Y" is written for the relevant exposure conditions, and "-" is written for the exposure conditions that are not applicable.
  • Exposed with a first light source after applying the first ink means that exposure was performed using the first light source (first exposure step) after applying the first ink (first ink applying step; the same applies hereinafter).
  • a UV-LED irradiation device product name: "3 x 3 surface irradiation array for deep ultraviolet UV-LED evaluation, LED light source with a maximum emission wavelength of 280 nm, manufactured by Nikkiso Co., Ltd." was used.
  • the exposure conditions were 45 mW. The conditions were such that irradiation was performed for 10 seconds at an illuminance of /cm2.All exposures using the first light source were performed under these conditions.
  • Exposed using a second light source after applying the first ink means that exposure was performed using the second light source after applying the first ink.
  • a UV-LED irradiation device product name "GA5", LED light source with a maximum emission wavelength of 385 nm, manufactured by Kyocera Corporation
  • the exposure conditions were such that the light was irradiated for 1 second at an illuminance of 10 W/cm 2 . All exposures using the second light source were performed under these conditions.
  • Exposure with the first light source after applying the second ink means that exposure was performed using the first light source after applying the second ink (second ink applying step; the same applies hereinafter).
  • Exposed with a second light source after applying the second ink means that the second ink was applied and then exposed using the second light source (second exposure step).
  • Exposed with the second light source after applying the third ink means that the third ink was applied and then exposed using the second light source (second exposure step).
  • electro beam irradiation means that the base material to which the first ink and the second ink have been applied is irradiated with an electron beam (electron beam irradiation step).
  • electron beam irradiation means that the base material to which the first ink, the second ink, and the third ink were applied was irradiated with an electron beam (electron beam irradiation step).
  • the electron beam was irradiated at an acceleration voltage of 90 KV and an irradiation dose of 60 KGy. All electron beam irradiations were performed under these conditions.
  • optical density (OD), adhesion, and migration amount were performed.
  • the evaluation method is as follows.
  • A The grid was not peeled off at all.
  • B The ratio (%) of the lattice peeling was more than 0% and less than 50%.
  • C The ratio (%) of the lattice peeling was more than 50%.
  • migration amount An image sample with an area of 0.01 m 2 (1 dm 2 ) was cut out from the image in the image recording material. 10 mL of ethanol was dropped onto the surface of the cut out image sample. The sample to which ethanol had been added was placed in a sealed glass container and left at 40° C. for 10 days. After standing for 10 days, the amount of elution from the image sample into ethanol (hereinafter referred to as "migration amount”) was measured. The amount of migration was measured by volatilizing the ethanol and measuring the mass of the remaining components after the sample had been left for 10 days. The evaluation criteria are as follows.
  • A The migration amount is 3 mg/dm 2 or less.
  • B The migration amount is more than 3 mg/dm 2 and less than 10 mg/dm 2 .
  • C Migration amount is more than 10 mg/dm 2 .
  • optical density (OD)> The optical density (OD) of the image surface of the image recording material was measured using a fluorescence spectrodensitometer (product name "FD-7", manufactured by Konica Minolta, Inc.). The evaluation criteria are as follows.
  • Tables 1 and 2 The evaluation results are shown in Tables 1 and 2.
  • Tables 1 and 2 the types of each ink used in Examples and Comparative Examples are listed. Furthermore, for each ink, if a specific hydrogen abstraction type polymerization initiator or amine is contained, "Y" is written, and if not, "-" is written.
  • Examples 1-1 and 1-2 include the step of applying a first ink containing a polymerizable compound and a first hydrogen abstraction type polymerization initiator onto a substrate; a step of exposing the base material to which the ink has been applied using a first light source; and a second ink containing a polymerizable compound and a second hydrogen abstraction type polymerization initiator on the area to which the first ink has been applied.
  • Comparative Example 1-1 and Comparative Example 1-4 do not include the step of exposing using the first light source and the step of exposing using the second light source, so the effect of suppressing migration is small. Ta.
  • the first ink did not contain the first hydrogen abstraction type polymerization initiator, so the adhesion of the image to the substrate was poor and the effect of suppressing migration was small.
  • Comparative Example 1-3 it was found that the adhesion of the image to the substrate was poor. This is because the first ink contains a second hydrogen abstraction type polymerization initiator, and by exposing it to the second light source after applying the first ink and after applying the second ink, the first ink is This is thought to be due to a decrease in the amount of polymerizable compounds in the ink film.
  • Comparative Example 1-5 the effect of suppressing migration was small because the step of exposing the base material to which the first ink was applied was not included.
  • Comparative Example 1-6 the second light source was used to expose the substrate to which the first ink was applied, so the effect of suppressing migration was small.
  • Examples 2-1 and 2-2 include the steps of applying a first ink containing a polymerizable compound and a first hydrogen abstraction type polymerization initiator onto a substrate; a step of exposing the base material to which the ink has been applied using a first light source; and a second ink containing a polymerizable compound and a second hydrogen abstraction type polymerization initiator on the area to which the first ink has been applied.
  • using an inkjet recording method exposing the base material to which the first ink and the second ink have been applied using a second light source, and the area to which the first ink and the second ink have been applied.
  • a step of applying a third ink containing a polymerizable compound and a second hydrogen abstraction type polymerization initiator onto the substrate using an inkjet recording method, and a step of applying the first ink, the second ink, and the third ink to the substrate includes the step of exposing using a second light source and the step of irradiating the base material to which the first ink, the second ink, and the third ink are applied with an electron beam, so the migration is different from the comparative example. It was found that it was possible to record an image that was suppressed compared to the above and had excellent adhesion to the base material.
  • Comparative Examples 2-1 and 2-4 do not include the step of exposing using the first light source and the step of exposing using the second light source, so the effect of suppressing migration is small. Ta.
  • the first ink did not contain the first hydrogen abstraction type polymerization initiator, so the effect of suppressing migration was small.
  • Comparative Example 2-3 it was found that the adhesion of the image to the substrate was poor. This is because the first ink contains a second hydrogen abstraction type polymerization initiator, and by exposing it to a second light source after applying the first ink, after applying the second ink, and after applying the third ink, an electronic This is thought to be because the amount of the polymerizable compound in the first ink film was reduced before the radiation irradiation.
  • Comparative Example 2-5 does not include the step of exposing the base material to which the first ink has been applied, and the step of exposing the base material to which the first ink and the second ink have been applied. , the effect of suppressing migration was small.

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Abstract

La présente invention concerne un procédé d'impression d'image comprenant : une étape consistant à fournir une première encre contenant un composé polymérisable et un premier initiateur de polymérisation de type à abstraction d'hydrogène sur un substrat ; une étape consistant à rendre visible le substrat pourvu de la première encre à l'aide d'une première source de lumière ayant une longueur d'onde d'émission maximale dans une plage de longueurs d'onde inférieure ou égale à 350 nm ; une étape consistant à fournir, par un procédé d'impression à jet d'encre et dans une région où la première encre a été fournie, une seconde encre contenant un composé polymérisable et un second initiateur de polymérisation de type à abstraction d'hydrogène ; une étape consistant à rendre visible le substrat pourvu de la première encre et de la seconde encre à l'aide d'une seconde source de lumière dans laquelle la longueur d'onde d'émission maximale située plus loin sur le côté de courte longueur d'onde est supérieure à 350 nm ; et une étape consistant à exposer au rayonnement des faisceaux d'électrons le substrat pourvu de la première encre et de la seconde encre.
PCT/JP2022/043642 2022-03-23 2022-11-25 Procédé d'impression d'image WO2023181502A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011178142A (ja) * 2010-03-04 2011-09-15 Seiko Epson Corp 印刷方法
WO2016158209A1 (fr) * 2015-03-31 2016-10-06 富士フイルム株式会社 Procédé de formation de film durci, procédé d'enregistrement d'image par jet d'encre, et matière imprimée
WO2017056860A1 (fr) * 2015-09-30 2017-04-06 コニカミノルタ株式会社 Jeu d'encres et procédé de formation d'images
JP2018188581A (ja) * 2017-05-10 2018-11-29 コニカミノルタ株式会社 活性光線硬化型インクジェットインク

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011178142A (ja) * 2010-03-04 2011-09-15 Seiko Epson Corp 印刷方法
WO2016158209A1 (fr) * 2015-03-31 2016-10-06 富士フイルム株式会社 Procédé de formation de film durci, procédé d'enregistrement d'image par jet d'encre, et matière imprimée
WO2017056860A1 (fr) * 2015-09-30 2017-04-06 コニカミノルタ株式会社 Jeu d'encres et procédé de formation d'images
JP2018188581A (ja) * 2017-05-10 2018-11-29 コニカミノルタ株式会社 活性光線硬化型インクジェットインク

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