WO2016158209A1 - Procédé de formation de film durci, procédé d'enregistrement d'image par jet d'encre, et matière imprimée - Google Patents

Procédé de formation de film durci, procédé d'enregistrement d'image par jet d'encre, et matière imprimée Download PDF

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Publication number
WO2016158209A1
WO2016158209A1 PCT/JP2016/056895 JP2016056895W WO2016158209A1 WO 2016158209 A1 WO2016158209 A1 WO 2016158209A1 JP 2016056895 W JP2016056895 W JP 2016056895W WO 2016158209 A1 WO2016158209 A1 WO 2016158209A1
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Prior art keywords
ink composition
composition
curable ink
active energy
image
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PCT/JP2016/056895
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English (en)
Japanese (ja)
Inventor
美里 佐々田
俊之 幕田
貴文 中山
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富士フイルム株式会社
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Publication of WO2016158209A1 publication Critical patent/WO2016158209A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • 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

Definitions

  • the present invention relates to a cured film forming method, an inkjet image recording method, and a printed matter.
  • an image recording method for forming an image on a recording medium such as paper based on an image data signal there are an electrophotographic method, a sublimation type and a melt type thermal transfer method, an ink jet method and the like.
  • the ink jet method is an inexpensive printing apparatus and does not require a plate at the time of printing, and the ink composition is ejected only on the required image portion to form an image directly on a recording medium. It can be used efficiently, and the running cost is low especially for small lot production. Furthermore, it has low noise and is excellent as an image recording method, and has attracted attention in recent years.
  • an ink composition for ink jet recording (a radiation curable ink composition for ink jet recording) that can be cured by irradiation with radiation such as ultraviolet rays is cured by irradiation with radiation such as ultraviolet rays, and most of the components of the ink composition are cured.
  • the solvent-based ink composition it is excellent in drying property and is difficult to bleed, so that it can be printed on various recording media.
  • the problem to be solved by the present invention is a cured film forming method capable of obtaining a cured film having excellent adhesion to a substrate and a small amount of residual monomer, and an inkjet image recording method excellent in image quality using the cured film And providing printed matter.
  • ⁇ 1> 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 active energy rays.
  • a cured film forming method wherein at least an electron beam having an acceleration voltage of 130 kV or less is used as an active energy ray in the step, and the electron beam is irradiated in the irradiation step so as to have an absorbed dose of 20 to 75 kGy; ⁇ 2> The cured film forming method according to ⁇ 1>, wherein in the composition application step, a droplet of a curable ink composition containing a polymerizable compound is ejected to form an image on a recording medium.
  • ⁇ 3> The irradiation step described in ⁇ 2>, wherein the irradiation step includes an active energy ray irradiation step of irradiating the image with an active energy ray having a wavelength of 250 to 400 nm, and an electron beam irradiation step of irradiating the image with an electron beam.
  • Cured film forming method, ⁇ 4> The cured film forming method according to ⁇ 2> or ⁇ 3>, including an undercoat step of forming an undercoat layer on the recording medium before the composition applying step, ⁇ 5>
  • the curable ink composition contains 0.5 to 15% by mass of a photopolymerization initiator having a molecular weight of 1,000 or more with respect to the total mass of the curable ink composition.
  • the cured film forming method according to any one of ⁇ 6> The curable ink composition does not contain a photopolymerization initiator having a molecular weight of less than 1,000, or the content of the photopolymerization initiator having a molecular weight of less than 1,000 is all of the curable ink composition.
  • the curable ink composition does not contain a volatile solvent, or the content of the volatile solvent exceeds 0% by mass and is 1% by mass or less with respect to the total mass of the curable ink composition.
  • the cured film forming method according to any one of ⁇ 2> to ⁇ 6>, ⁇ 8>
  • the polyfunctional polymerizable compound having one or more (meth) acryloyl groups in the molecule as the polymerizable compound is 75 with respect to the total mass of the curable ink composition.
  • the cured film forming method according to any one of ⁇ 2> to ⁇ 7>, including at least mass%, ⁇ 9>
  • an energy ray irradiation step an image forming step of forming an image by discharging droplets of a curable ink composition containing a polymerizable compound onto the undercoat layer irradiated with active energy rays, and the irradiation step
  • An active energy ray irradiation step an image forming step of forming an image by discharging droplets of a curable ink composition containing a polymerizable compound on the undercoat layer irradiated with the active energy ray, and the above
  • an image formed with the curable ink composition and a second active energy ray irradiating step for irradiating the undercoat layer with active energy rays and as the irradiating step, formed with the curable ink composition.
  • An inkjet image forming method using the cured film forming method according to any one of ⁇ 1> to ⁇ 10>, ⁇ 12> A printed material on which a cured film is formed by the method for forming a cured film according to any one of ⁇ 1> to ⁇ 10>.
  • a cured film forming method capable of obtaining a cured film having excellent adhesion to a substrate and a small amount of residual monomer, and an inkjet image recording method and printed matter excellent in image quality using the cured film. can do.
  • (meth) acrylate represents acrylate and methacrylate
  • (meth) acryl represents acryl and methacryl
  • (meth) acryloyl represents acryloyl and methacryloyl.
  • mass% and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the polymer component is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.
  • the cured film forming method of the present invention includes a composition applying step for applying a curable composition containing a polymerizable compound on a recording medium, and an irradiation step for irradiating the curable composition with two or more active energy rays. And at least an electron beam having an acceleration voltage of 130 kV or less is used as the active energy ray in the irradiation step, and the electron beam is irradiated in the irradiation step so that the absorbed dose is 20 to 75 kGy. .
  • absorbed dose refers to the absorbed dose of the curable composition (image) in electron beam irradiation.
  • the “cured film” refers to a film formed by curing a curable composition containing a polymerizable compound on a recording medium. For example, droplets of the curable ink composition are recorded on the recording medium. It includes a cured image formed by discharging onto the recording medium, an undercoat layer cured by applying a curable undercoat liquid onto the recording medium, and the like.
  • Preferred embodiments of the cured film forming method of the present invention include the following first embodiment or the following second embodiment.
  • the first embodiment of the cured film forming method of the present invention includes a step of ejecting droplets of a curable ink composition containing a polymerizable compound to form an image on a recording medium, and two or more types of the image.
  • the cured image formed on the recording medium corresponds to the cured film.
  • the second embodiment of the cured film forming method of the present invention includes a step of applying a curable composition on a recording medium to form an undercoat layer, and an active energy ray irradiating step of irradiating the undercoat layer with an active energy ray.
  • an electron beam irradiation step of irradiating an electron beam with an acceleration voltage of 110 kV or less.
  • the electron beam is irradiated so as to have an absorbed dose of 20 to 75 kGy.
  • the cured undercoat layer formed on the recording medium corresponds to the cured film.
  • the cured film forming method of the present invention is particularly preferable as an inkjet image recording method, suitable for package printing, and particularly suitable for package printing for food packaging.
  • the “image” in the present invention includes not only a general image such as a photograph or a picture but also a solid image, characters, and other information.
  • the composition applying step a step of applying a curable composition containing a polymerizable compound on a recording medium to form an undercoat layer, and the irradiation
  • an active energy ray irradiating step for irradiating the undercoat layer with active energy rays, and droplets of a curable ink composition containing a polymerizable compound are ejected onto the undercoat layer irradiated with the active energy rays.
  • the image forming step for forming an image and the electron beam irradiation step for irradiating the image and the undercoat layer with an electron beam having an acceleration voltage of 130 kV or less are preferably included as the irradiation step.
  • a curable composition containing a polymerizable compound is applied on a recording medium to form an undercoat layer.
  • Printing for food packaging and the like requires low residual monomer and high productivity in addition to high image quality and high adhesion.
  • a low molecular initiator or the like is used to obtain sufficient curability, a plurality of times of curing with ultraviolet rays is used, and an electron beam is used. Irradiation has been devised to increase curability by using a high acceleration voltage, but it is insufficient to obtain sufficient film quality (rub resistance) during high-speed printing, and the amount of residual monomer has also been a problem.
  • the present inventors have found that the amount of residual monomer is small by using a specific electron beam for curing the ink composition or for curing the undercoat layer and the ink composition. It has been found that an image having excellent adhesion to the material and image quality can be obtained.
  • the cured film formation method of this invention includes the composition provision process which provides the curable composition containing a polymeric compound on a recording medium.
  • the curable composition include a curable ink composition containing a polymerizable compound (also simply referred to as “ink composition”) and an undercoat curable composition containing a polymerizable compound (also referred to as “undercoat composition”). Preferred).
  • the composition applying step in the cured film forming method of the present invention is a step of forming an image on a recording medium by discharging droplets of the curable ink composition containing a polymerizable compound. It is preferable.
  • the composition applying step in the cured film forming method of the present invention is preferably a step of forming an undercoat layer by applying a curable composition containing a polymerizable compound onto a recording medium.
  • the ink composition that can be used in the composition application step include curable ink compositions described later.
  • the undercoat composition mentioned later is mentioned suitably.
  • the recording medium (base material, support, etc.) used in the cured film forming method of the present invention is not particularly limited, and a known recording medium can be used. Among these, a transparent recording medium is preferable for printing food packaging packages for soft packaging.
  • “transparent” means that the visible light transmittance is 80% or more, and the visible light transmittance is preferably 90% or more.
  • a transparent recording medium may be colored as long as it is transparent, but is preferably a colorless recording medium.
  • the recording medium include glass, quartz, plastic film (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, acrylic resin, chlorinated polyolefin resin, poly Ether sulfone resin, polyethylene terephthalate (PET), polyethylene naphthalate, nylon, polyethylene, polystyrene, polypropylene, polycycloolefin resin, polyimide resin, polycarbonate resin, polyvinyl acetal, and the like.
  • the transparent recording medium may be a mixture of two or more of these resins, or a laminate of two or more of these resins.
  • the recording medium is preferably a recording medium having an image forming surface made of at least one resin selected from the group consisting of polyolefin resin, polyester resin and polyamide resin, and includes polyethylene terephthalate, polyethylene, polypropylene, and More preferably, the recording medium has an image forming surface made of at least one resin selected from the group consisting of nylon, and at least one resin selected from the group consisting of polyethylene terephthalate, polyethylene, polypropylene and nylon.
  • the recording medium is made of As polyethylene, LDPE (low density polyethylene), MDPE (medium density polyethylene), HDPE (high density polyethylene), and polypropylene as CPP (unstretched polypropylene), OPP (biaxially stretched polypropylene), KOP (polyvinylidene chloride coating) As the OPP), AOP (PVA-coated OPP), and polyethylene terephthalate, biaxially stretched polyester and nylon are preferably ON (stretched nylon), KON (stretched nylon), and CN (unstretched nylon).
  • EVA ethylene / vinyl acetate copolymer film
  • PVA vinyl acetate copolymer film
  • PVC polyvinyl chloride
  • PVDC polyvinylidene chloride, saran
  • cellophane PT, MST, K cello
  • ZX Zecron (polyacrylonitrile, PAN)
  • PS polystyrene, styrene
  • AL aluminum foil
  • VM film aluminum vapor-deposited film, transparent vapor-deposited film
  • a co-extruded film in which a resin is extruded from two or more parallel slits to form a film and laminate at the same time is also preferably used. Even films as thin as a few ⁇ m that cannot be made into a film can be laminated to a maximum of 5 to 7 layers.
  • the thickness of the recording medium is not particularly limited, but is preferably 1 to 500 ⁇ m, more preferably 2 to 200 ⁇ m, still more preferably 5 to 100 ⁇ m, and 10 to 90 ⁇ m. Is particularly preferred.
  • the curable ink composition is preferably ejected by an inkjet method.
  • an ink jet head is preferably used.
  • an inkjet head for example, a charge control method that ejects ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element, and an electrical signal is converted into an acoustic beam into ink
  • a head such as an acoustic ink jet system that irradiates and discharges ink using radiation pressure, or a thermal ink jet (bubble jet (registered trademark)) system that uses ink to form bubbles by heating the ink is suitable. is there.
  • the ink jet recording apparatus that can be used in the cured film forming method of the present invention is not particularly limited, and a known ink jet recording apparatus that can achieve a desired resolution can be arbitrarily selected and used. That is, any known inkjet recording apparatus including a commercially available product can discharge the ink composition onto the recording medium in the image forming step of the inkjet recording method of the present invention.
  • Examples of the ink jet recording apparatus that can be used in the present invention include an apparatus including an ink supply system, a temperature sensor, and an active energy ray source.
  • the ink supply system includes, for example, an original tank containing an ink composition, 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 a multi-size dot of 1 to 100 pl, more preferably 8 to 30 pl, preferably 320 ⁇ 320 to 4,000 ⁇ 4,000 dpi, more preferably 400 ⁇ 400 to 1,600 ⁇ . It can be driven so as to discharge at a resolution of 1,600 dpi, more preferably 600 ⁇ 600 to 1,200 ⁇ 1,200 dpi.
  • dpi represents the number of dots per 2.54 cm.
  • the total droplet ejection amount per unit area of the curable ink composition is preferably 0.001 to 10 g / m 2 , and 0.01 more preferably ⁇ a 9 g / m 2, particularly preferably 0.5 ⁇ 8g / m 2.
  • the total droplet ejection amount per unit area of the curable ink composition is preferably 0.001 to 10 g / m 2 , and 0.01 more preferably ⁇ a 9 g / m 2, particularly preferably 0.5 ⁇ 8g / m 2.
  • the ink jet recording apparatus preferably includes a means for stabilizing the ink composition temperature.
  • the parts to be kept at a constant temperature are all the piping systems and members from the ink tank (intermediate tank if there is an intermediate tank) to the nozzle ejection surface. That is, heat insulation and heating can be performed from the ink supply tank to the inkjet head portion.
  • the temperature control method is not particularly limited, but for example, it is preferable to provide a plurality of temperature sensors at each piping site and perform heating control according to the ink flow rate and the environmental temperature.
  • the temperature sensor can be provided near the ink supply tank and the nozzle of the inkjet head.
  • the head unit to be heated is thermally shielded or insulated so that the apparatus main body is not affected by the temperature from the outside air.
  • the temperature control range of the ink composition is preferably set to ⁇ 5 ° C. of the set temperature, more preferably ⁇ 2 ° C. of the set temperature, and further preferably set temperature ⁇ 1 ° C. .
  • the droplet ejection interval from the application of the undercoating composition to the first droplet ejection of the ink composition is 10 ⁇ s or more. It is preferably 2 seconds or less, more preferably 10 ⁇ s or more and 5 seconds or less, and particularly preferably 20 ⁇ s or more and 5 seconds or less.
  • a curable ink composition may be used individually by 1 type, or 2 or more types may be used.
  • a color image it is preferable to use at least each color ink composition of yellow, cyan, magenta, and black, and more preferable to use each color ink composition of white, yellow, cyan, magenta, and black.
  • a light color ink composition such as light magenta or light cyan, a special color ink composition such as orange, green and violet, a clear ink composition, a metallic ink composition, or the like may be used.
  • the inkjet recording method of the present invention includes a step of ejecting the curable ink composition for each curable ink composition to be used, and irradiating the ejected curable ink composition with active energy rays. It is preferable to include a step of semi-curing. The effect of this invention can be exhibited more as it is the said aspect. The step of semi-curing by irradiation with the active energy ray is included in the irradiation step described later.
  • the order of the curable ink compositions ejected by the inkjet method is not particularly limited, but it is preferable to apply the curable ink composition having a low lightness to the recording medium, and yellow, cyan, magenta, and black. When used, it is preferably applied on the recording medium in the order of black ⁇ magenta ⁇ cyan ⁇ yellow. In addition, when white is added to this, it is preferable to apply it on the recording medium in the order of black ⁇ magenta ⁇ cyan ⁇ yellow ⁇ white. Furthermore, the present invention is not limited to this, and the ink set of the present invention including at least seven colors of yellow, light cyan, light magenta, cyan, magenta, black and white ink compositions can be preferably used. In this case, it is preferable to apply the recording material in the order of black ⁇ magenta ⁇ cyan ⁇ yellow ⁇ light magenta ⁇ light cyan ⁇ white.
  • the cured film forming method of the present invention includes an irradiation step of irradiating the curable composition applied in the composition applying step with two or more kinds of active energy rays, and an acceleration voltage is used as the active energy rays in the irradiation step. At least an electron beam of 130 kV or less is used, and in the irradiation step, the electron beam is irradiated so that the absorbed dose is 20 to 75 kGy.
  • the irradiation step is preferably a step of sequentially irradiating the image with “active energy rays other than electron beam” and “electron beam”, and irradiating with “active energy rays other than electron beam” on the curable composition.
  • an active energy ray irradiating step and an electron beam irradiating step of irradiating the curable composition irradiated with the active energy ray with an electron beam are considered to reach the lowermost layer (the curable composition in contact with the recording medium) even when the two or more curable compositions are applied and laminated.
  • active energy rays other than electron beams include ⁇ rays, ⁇ rays, X rays, ultraviolet rays, visible light, and infrared rays.
  • the active energy ray irradiation step it is preferable to irradiate at least an active energy ray having a wavelength of 250 to 400 nm.
  • the image forming step when two or more curable ink compositions are discharged, after discharging one curable ink composition, before discharging the next other curable ink composition. It is preferable that the method further includes a step of irradiating an active energy ray to an image formed by the discharged curable ink composition. That is, when two or more curable ink compositions are ejected in the composition application step, an image formed with a curable ink composition other than the “curable ink composition with the last droplet ejection order” is used.
  • an active energy ray having a wavelength of 250 to 400 nm it is preferable to include a step of irradiating an electron beam after image formation is completed with the curable ink composition to be discharged last. Further, it may include a step of irradiating with an active energy ray having a wavelength of 250 to 400 nm and then irradiating an electron beam after image formation is completed with the curable ink composition to be discharged last.
  • an exposure light source (active energy ray source) of active energy rays in the irradiation process mercury lamps, gas / solid lasers, etc. are mainly used, and light sources used for curing ink compositions for photo-curable ink jet recording.
  • mercury lamps and metal halide lamps are widely known.
  • mercury-free is strongly desired, and replacement with a GaN-based semiconductor ultraviolet light-emitting device is very useful industrially and environmentally.
  • LED (UV-LED) and LD (UV-LD) are small, have a long lifetime, high efficiency, and low cost, and are expected as light sources for photo-curing inkjet.
  • a light emitting diode LED
  • LD laser diode
  • Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. If even shorter wavelengths are required, for example, LEDs disclosed in US Pat. No. 6,084,250 can emit active rays centered between 300 nm and 370 nm can be used. . Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands.
  • the UV source particularly preferred in the present invention is a UV-LED.
  • the maximum illumination intensity on the LED recording medium is preferably 10 ⁇ 2,000mW / cm 2, more preferably 20 ⁇ 1,000mW / cm 2, is 50 ⁇ 800mW / cm 2 It is particularly preferred.
  • Suitable examples of ultraviolet exposure means include a metal halide lamp, a mercury lamp, and an LED. Among these, LED is preferable.
  • the ink jet recording method of the present invention is suitable for a soft packaging package, and it is preferable to use a recording medium having a relatively thin film thickness as described above. In this case, it is preferable to use an LED because the deformation and shrinkage of the recording medium due to heat are suppressed.
  • a maleimide compound particularly a curable ink composition containing a compound having a molecular weight of 1,000 or more and having two or more maleimide structures in the molecule, or a high thioxanthone skeleton is used.
  • the active energy having a peak wavelength at 400 nm or less in the irradiation step It is preferable to irradiate ultraviolet rays having a peak wavelength of 200 to 380 nm, and more preferable to irradiate ultraviolet rays having a peak wavelength of 250 to 320 nm.
  • the ultraviolet irradiation means having a peak wavelength of 400 nm or less an LED is preferable.
  • An electron beam is an electron particle beam.
  • at least an electron beam having an acceleration voltage of 130 kV or less is used, and the electron beam is irradiated so that the absorbed dose is 20 to 75 kGy.
  • An electron beam exposure means A well-known electron beam irradiation apparatus and an electron beam accelerator can be used.
  • As the electron beam irradiation apparatus and the electron beam accelerator a scanning method, a double scanning method, or a curtain beam method can be adopted, and a curtain beam method that can obtain a large output at a relatively low cost can be adopted.
  • the acceleration voltage of the electron beam used in the irradiation step is 130 kV or less, preferably 30 to 130 kV, more preferably 50 to 110 kV, still more preferably 70 to 110 kV, and more preferably 80 to 110 kV. It is particularly preferred. Within the above range, the amount of residual monomer in the obtained printed product can be further reduced.
  • the electron beam used for irradiating the image in the irradiation step needs to be irradiated so that the absorbed dose is 20 to 75 kGy, and is preferably irradiated so that the absorbed dose is 30 to 60 kGy, and the absorbed dose is 30 to 50 kGy. It is more preferable to irradiate.
  • the electron beam may be irradiated only once or twice or more, but it is preferable to perform the irradiation only once. Further, when the electron beam is irradiated twice or more, it is preferable that the electron beam irradiated to the image is irradiated so that the total absorbed dose is 20 to 75 kGy.
  • the irradiation time of the electron beam is not particularly limited as long as it satisfies the above absorbed dose.
  • the atmosphere in which the electron beam is irradiated is not particularly limited, but the oxygen concentration is preferably 2% by volume or less, the oxygen concentration is more preferably 1% by volume or less, and the oxygen concentration is further 300 ppm or less. preferable. It is excellent in sclerosis
  • the oxygen concentration is preferably adjusted by nitrogen purge.
  • UV / EB curing technology (1982, issued by General Technology Center Co., Ltd.) and “Applied technology of low energy electron beam irradiation” (2000, The well-known thing described in (CMC issuance) etc. can be used.
  • the irradiation step includes a step of irradiating an active energy ray and semi-curing the image formed with the curable ink composition or the undercoat layer formed with the curable composition for undercoat.
  • the cured film forming method of the present invention when two or more curable compositions are applied, after one curable composition is applied, the other one curable ink composition is discharged. It is preferable to include a step of irradiating an active energy ray to the image or the undercoat layer formed from the discharged curable composition and semi-curing it, respectively.
  • the image formed with the applied curable composition may or may not be subjected to a semi-curing step by irradiating active energy rays.
  • the method for semi-curing the curable composition is not particularly limited, but the following methods can be preferably exemplified.
  • “semi-cured” means partially cured (partially cured) and refers to a state where the curable composition is partially cured but not completely cured.
  • the degree of curing may be non-uniform.
  • the curable composition is preferably cured in the depth direction.
  • Examples of the method for semi-curing the curable composition include known thickening methods such as a method for causing the semi-curing reaction by applying an active energy ray or heat to the curable composition.
  • the method of causing a semi-curing reaction by applying an active energy ray or heat is a method of insufficiently carrying out the polymerization reaction of the polymerizable compound on the surface of the ink composition applied to the recording medium.
  • the curable composition applied on the recording medium is more cured. It progresses and the surface hardening tends to be delayed.
  • the curable composition can be semi-cured by controlling the active energy ray or heat application conditions.
  • the applied curable composition is preferably semi-cured by irradiation with an active energy ray having a wavelength of 250 to 400 nm.
  • the amount of energy required for semi-curing the curable composition varies depending on the type and content of the polymerization initiator, but is preferably 1 to 500 mJ / cm 2 when energy is applied by active energy rays. When energy is applied by heating, it is preferable to heat the recording medium for 0.1 to 1 second under the condition that the surface temperature of the recording medium is in the temperature range of 40 to 80 ° C.
  • active energy rays or heat such as ultraviolet rays and heating
  • active energy rays or heat promotes the generation of active species due to decomposition of the polymerization initiator, and also increases the active species and raises the temperature, resulting in polymerizability or crosslinkability due to the active species.
  • the curing reaction by polymerization or crosslinking of the material is accelerated.
  • thickening viscosity increase
  • the unpolymerization rate can be quantitatively measured by the reaction rate of the ethylenically unsaturated group or the cyclic ether group, as will be described later.
  • the unpolymerized rate (A ( After polymerization) / A (before polymerization)) is preferably 0.2 or more and 0.9 or less, more preferably 0.3 or more and 0.9 or less, and 0.5 or more and 0.9 or less. It is particularly preferred.
  • a (after polymerization) is the absorbance of the infrared absorption peak due to the polymerizable group after the polymerization reaction
  • a (before polymerization) is the absorbance of the infrared absorption peak due to the polymerizable group before the polymerization reaction.
  • the polymerizable compound contained in the ink composition is an acrylate monomer or a methacrylate monomer
  • an absorption peak based on a polymerizable group acryloyloxy group, methacryloyloxy group
  • the polymerizable compound is an oxetane compound
  • an absorption peak based on a polymerizable group oxetanyl group
  • the polymerizable compound is an epoxy compound
  • an absorption peak based on a polymerizable group epoxy group
  • the unpolymerization rate is preferably defined by the absorbance of the peak.
  • a commercially available infrared spectrophotometer can be used, which may be either a transmission type or a reflection type, and is preferably selected as appropriate in the form of a sample.
  • it can be measured using an infrared spectrophotometer FTS-6000 manufactured by BIO-RAD.
  • an irradiation process includes the process of irradiating an electron beam to the said image and carrying out complete hardening.
  • “fully cured” refers to a state in which the inside and the surface of the undercoat liquid and the ink composition on the recording medium are completely cured.
  • plain paper for example, copy paper C2 manufactured by Fuji Xerox Co., Ltd., product code V436
  • plain paper for example, copy paper C2 manufactured by Fuji Xerox Co., Ltd., product code V436
  • plain paper for example, copy paper C2 manufactured by Fuji Xerox Co., Ltd., product code V436
  • the recording medium conveyance speed that is, the printing speed is preferably 5 m / min to 300 m / min, more preferably 20 m / min to 200 m / min, and 25 m / min to 100 m. / Min is more preferable, and 25 to 50 m / min is particularly preferable.
  • the cured film forming method of the present invention is excellent in adhesion to a substrate and image quality even during high-speed printing as described above, and can obtain an image with a small amount of residual monomer.
  • the cured film forming method of the present invention includes an undercoat step of forming an undercoat layer on the recording medium before the composition applying step, or curing in the composition applying step.
  • the adhesive composition is preferably an undercoat composition.
  • limiting in particular as said undercoat composition Although a well-known thing can be used, It is preferable to use the undercoat composition mentioned later.
  • a coating apparatus or an inkjet nozzle can be used, and a coating apparatus is preferably used.
  • the coating device According to the objective etc., it can select suitably according to the objective etc., for example, an air doctor coater, a blade coater, a lot coater, a knife coater, a squeeze coater, an impregnation coater , Reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, cast coater, spray coater, curtain coater and extrusion coater.
  • an air doctor coater for example, an air doctor coater, a blade coater, a lot coater, a knife coater, a squeeze coater, an impregnation coater , Reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, cast coater, spray coater, curtain coater and extrusion coater.
  • the application of the undercoat composition onto the recording medium is preferably performed using a relatively inexpensive bar coater or spin coater.
  • the undercoat composition is preferably applied to the same area as the image formed by discharging the curable ink composition on the recording medium in the image forming step or to an area wider than the above image, and covers the entire area where the image can be formed. It is preferable to be provided so as to cover.
  • the application amount (mass per unit area) of the undercoat composition is preferably 0.05 to 5 g / m 2 , and more preferably 0.06 to 3 g / m 2 . When the application amount of the undercoat composition is within the above range, a sufficient adhesion improving effect can be obtained and a printed matter having excellent flexibility can be obtained.
  • the amount of the undercoat composition applied is within a range of 0.05 to 5 when the maximum amount of ink composition applied per unit area (per color) is 1. It is preferably within a range of 0.07 to 4, more preferably within a range of 0.1 to 3.
  • the undercoat layer when an undercoat layer is formed by applying a curable composition on a recording medium, it is preferable that the undercoat layer is semi-cured in the irradiation step.
  • the method of semi-curing the undercoat layer is not particularly limited, and includes a method of semi-curing with heat or active energy rays. A method of causing it is preferable.
  • the amount of energy required for semi-curing the undercoat layer varies depending on the composition, particularly the type and content of the polymerization initiator, but is preferably 1 to 500 mJ / cm 2 .
  • the semi-curing of the undercoat layer can be performed in the same manner as the semi-curing of the curable ink composition, and the exposure apparatus used, the exposure conditions, and the preferred mode are also the same.
  • the process of semi-hardening an undercoat layer it is preferable to harden an undercoat layer completely by irradiation of the electron beam in an irradiation process.
  • the cured film forming method of the present invention preferably further includes a laminating step of forming at least an adhesive layer and a laminated film on the cured film, preferably an image, after the irradiation step.
  • the laminating step is more preferably a laminating step in which an adhesive layer and a laminate film are formed on the entire surface of the recording medium on the cured film side.
  • a resin film is preferably used, and examples thereof include a polyethylene terephthalate film, a polypropylene film, a nylon film, a polyvinyl chloride film, a polyethylene film, and a triacetyl cellulose film. Moreover, those films may be biaxially stretched.
  • the laminate film may be bonded after the adhesive layer is formed on the image, or may be bonded on the image after the adhesive layer is first applied to the laminate film.
  • a laminating method a known method can be used without any particular limitation, and dry lamination can be exemplified.
  • a resin film is used as the base material, it is preferable to use a resin film having high adhesiveness with the resin film used on the surface on which the base material is laminated, although it depends on the laminating method selected. .
  • the ink jet recording apparatus preferably used in the present invention will be further described in detail.
  • the ink jet recording apparatus suitably used in the present invention is not particularly limited as long as it has an active energy ray irradiating means for irradiating an active energy ray and an electron beam irradiating means for irradiating an electron beam.
  • Conveying means for conveying a medium; applying means for applying an undercoat composition on the recording medium; discharge means for inkjet discharging a curable ink composition onto the undercoat composition; and active energy rays having a wavelength of 250 to 400 nm.
  • the ink jet recording apparatus of the present invention is preferably a so-called single pass ink jet recording apparatus.
  • FIG. 1 is a schematic diagram showing an example of an ink jet recording apparatus preferably used in the present invention.
  • the following apparatus has the active energy ray source 17 for undercoat composition semi-hardening, even if it is an apparatus which does not have such a semi-hardening light source, it can be used conveniently for this invention.
  • the recording medium 12 stretched by the delivery roller 24 and the take-up roller 26 that is the conveying means of the recording medium 12 is conveyed in the direction of arrow A, and the undercoat composition is applied by the undercoat composition application roller 14. Subsequently, the undercoat composition is semi-cured by the active energy ray source 17 for semi-curing the undercoat composition. Subsequently, the ink compositions of the respective colors (K: black, Y: yellow, M: magenta, C: cyan, W: white) are ejected by the inkjet heads 18K, 18C, 18M, 18Y, and 18W that discharge the ink compositions of the respective colors.
  • the black, yellow, magenta and cyan ink compositions ejected by the semi-curing active energy ray sources 20K, 20C, 20M, and 20Y installed immediately after the inkjet heads 18K, 18C, 18M, and 18Y.
  • the semi-curing active energy ray sources 17, 20K, 20C, 20M, and 20Y are all ultraviolet exposure light sources.
  • the nitrogen purge electron beam irradiation unit 22 irradiates the recording medium with an electron beam in an oxygen-poor atmosphere, and the semi-cured undercoat composition and ink composition are cured.
  • the electron beam source is surrounded by an inert gas blanket and connected to an inert gas generator via an inert gas pipe, and the inert gas generator is operated.
  • the aspect by which the air in a blanket is substituted by an inert gas is mentioned preferably.
  • nitrogen or the like can be used as the inert gas.
  • a nip roll 28 is provided to improve the conveyance accuracy. When the nip roll is used, more accurate transportability is realized, and registration deviation (landing position deviation) is suppressed.
  • the nip roll 28 is not essential, and an ink jet recording apparatus that does not have a nip roll may be used.
  • the cured film forming method of the present invention may further include other steps other than those described above. There is no restriction
  • the curable ink composition used in the present invention contains a polymerizable compound.
  • the curable ink composition used in the present invention is an oily liquid composition curable by an electron beam, and is preferably an oily liquid composition curable by an ultraviolet ray and an electron beam.
  • the curable ink composition used in the present invention is an electron beam curable ink composition, and is different from the water-based ink composition and the solvent ink composition.
  • the curable ink composition preferably contains as little water and volatile solvent as possible.
  • the curable ink composition preferably does not contain water, or the water content is more than 0% by mass and 1% by mass or less with respect to the total mass of the curable ink composition.
  • the content of water does not include water, or the content of water is more than 0% by mass and 0.5% by mass or less with respect to the total mass of the curable ink composition.
  • the water content is more preferably more than 0% by mass and 0.1% by mass or less with respect to the total mass of the curable ink composition.
  • the curable ink composition does not contain a volatile solvent, or the content of the volatile solvent is more than 0% by mass and 1% by mass or less with respect to the total mass of the curable ink composition.
  • the volatile solvent is not included, or the content of the volatile solvent is more than 0% by mass and 0.5% by mass or less with respect to the total mass of the curable ink composition.
  • the volatile solvent is not included, or the content of the volatile solvent is more preferably more than 0% by mass and 0.1% by mass or less with respect to the total mass of the curable ink composition.
  • the volatile solvent in the present invention is a solvent having a boiling point of 150 ° C. or lower.
  • the curable ink composition used in the present invention contains a polymerizable compound (also referred to as “monomer”).
  • the polymerizable compound may be a radical polymerizable compound or a cationic polymerizable compound, but is preferably a radical polymerizable compound.
  • the cationic polymerizable compound is not particularly limited, and a known cationic polymerizable compound can be used. From the viewpoint of curability and scratch resistance, a compound having an epoxy ring, a compound having an oxetane ring, and a vinyl ether compound are preferable. More preferred are compounds having an epoxy ring and compounds having an oxetane ring.
  • the radical polymerizable compound is not particularly limited, and a known ethylenically unsaturated compound can be used. Examples thereof include (meth) acrylate compounds, vinyl ether compounds, allyl compounds, N-vinyl compounds, and unsaturated carboxylic acids. .
  • a radical polymerizable monomer described in JP-A 2009-22214, a polymerizable compound described in JP-A 2009-209289, and an ethylenically unsaturated compound described in JP-A 2009-191183 are exemplified.
  • the polymerizable compound an ethylenically unsaturated compound is preferable, and a compound having a (meth) acryloyl group is more preferable.
  • the polymerizable compound in the curable ink composition preferably contains a polyfunctional polymerizable compound, more preferably contains a polyfunctional polymerizable compound having one or more (meth) acryloyl groups in the molecule. More preferably, it contains a bifunctional polymerizable compound having one or more (meth) acryloyl groups.
  • the curable ink composition contains 45% by mass or more of a polyfunctional polymerizable compound having one or more (meth) acryloyl groups in the molecule as a polymerizable compound, based on the total mass of the curable ink composition. It is preferable that the bifunctional polymerizable compound having one or more (meth) acryloyl groups in the molecule is contained in an amount of 75% by mass or more based on the total mass of the curable ink composition.
  • Examples of the polyfunctional polymerizable compound having one or more (meth) acryloyl groups in the molecule include di (meth) acrylic acid esters (bifunctional (meth) acrylate compounds) of aliphatic hydrocarbon diols having 6 to 12 carbon atoms.
  • the hydrocarbon diol may be any of a linear hydrocarbon diol, a branched hydrocarbon diol and a cyclic hydrocarbon diol, and a linear hydrocarbon diol and a branched hydrocarbon diol are preferably exemplified.
  • Di (meth) acrylic acid esters of aliphatic hydrocarbon diols having 6 to 12 carbon atoms are preferred because of their low viscosity.
  • di (meth) acrylic esters of aliphatic hydrocarbon diols having 6 to 12 carbon atoms examples include 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8- Octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 3-methyl-1, 5-pentanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, tricyclodecane dimethanol di (meth) Acrylate is preferably exemplified.
  • decanediol diacrylate, dodecanediol diacrylate, and 3-methyl-1,5-pentanediol dimethacrylate are more preferable, and 3-methyl-1,5-pentanediol diacrylate is still more preferable.
  • polyfunctional polymerizable compound having one or more (meth) acryloyl groups in the molecule include dipropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and neopentyl glycol diester.
  • the polyfunctional polymerizable compound having one or more (meth) acryloyl groups in the molecule preferably includes a compound having a vinyloxy group and a (meth) acryloxy group.
  • Particularly preferred examples of the compound having a vinyloxy group and a (meth) acryloxy group include 2- (2-vinyloxyethoxy) ethyl acrylate and 2- (2-vinyloxyethoxy) ethyl methacrylate.
  • Trifunctional or higher functional (meth) acrylate compounds include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, and trimethylol.
  • Examples include propane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, and oligoester (meth) acrylate.
  • a polyfunctional vinyl ether compound is included as a polymeric compound.
  • polyfunctional vinyl ether compounds include, for example, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide.
  • Divinyl ethers such as divinyl ether and bisphenol F alkylene oxide divinyl ether; trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pen Tavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol And polyfunctional vinyl ethers such as
  • a di- or trivinyl ether compound is preferable from the viewpoint of curability, adhesion to a recording medium, surface hardness of a formed image, and the like, a divinyl ether compound is more preferable, and a triethylene glycol divinyl ether is preferable. Particularly preferred.
  • the curable ink composition may contain a monofunctional ethylenically unsaturated compound as the polymerizable compound.
  • Monofunctional ethylenically unsaturated compounds include monofunctional (meth) acrylate compounds, monofunctional (meth) acrylamide compounds, monofunctional aromatic vinyl compounds, monofunctional vinyl ether compounds (such as triethylene glycol divinyl ether), monofunctional N- Examples thereof include vinyl compounds (N-vinylcaprolactam and the like).
  • the curable ink composition does not contain a monofunctional polymerizable compound as the polymerizable compound, or the content of the monofunctional polymerizable compound is 0% by mass with respect to the total mass of the curable ink composition.
  • a polymeric compound may be used individually by 1 type, or may use 2 or more types together.
  • the content of the polymerizable compound in the curable ink composition is preferably 10 to 95% by mass, and preferably 50 to 90% with respect to the total mass of the curable ink composition, from the viewpoint of both adhesion and blocking inhibition.
  • the mass is preferably 70% by mass, and more preferably 70 to 85% by mass.
  • the curable ink composition preferably contains a polymerization initiator.
  • a radical polymerizable compound it contains a radical polymerizable initiator, and when it contains a cationic polymerizable compound, it contains a cationic polymerization initiator. It is more preferable to contain.
  • a radical polymerization initiator is preferable.
  • the polymerization initiator in the present invention is preferably a photopolymerization initiator, and more preferably a photoradical polymerization initiator.
  • the cationic polymerization initiator or radical polymerization initiator in the present invention is a compound that generates a radical, acid, or base by causing a chemical change through the action of light or interaction with the electronically excited state of a sensitizing dye.
  • the photo radical generator or the photo acid generator is preferred from the viewpoint that polymerization can be initiated by a simple means of exposure.
  • a cationic polymerization initiator or radical polymerization initiator is appropriately selected from the polymerization initiators described in detail below in consideration of the relationship with the cationic polymerizable compound or radical polymerizable compound used in combination. Can be used.
  • Cationic polymerization initiators include onium salt compounds such as diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, and imides that decompose upon irradiation with ultraviolet rays and / or electron beams to generate acids.
  • Preferred examples include sulfonate compounds such as sulfonate, oxime sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl sulfonate.
  • the cationic polymerization initiator is preferably an aromatic onium salt, more preferably an iodonium salt or a sulfonium salt, and particularly preferably an iodonium PF 6 salt or a sulfonium salt PF 6 salt from the viewpoint of curability. .
  • the radical polymerization initiator is more preferably a radical photopolymerization initiator.
  • radical polymerization initiators include (a) aromatic ketones, (b) acylphosphine compounds, (c) aromatic onium salt compounds, (d) organic peroxides, (e) thio compounds, and (f) hexaary.
  • a rubiimidazole compound (g) a ketoxime ester compound, (h) a borate compound, (i) an azinium compound, (j) a metallocene compound, (k) an active ester compound, (l) a compound having a carbon halogen bond, and (m ) Alkylamine compounds and the like.
  • radical polymerization initiators the above compounds (a) to (m) may be used alone or in combination. Details of the radical polymerization initiator are described in, for example, paragraphs 0090 to 0116 of JP2009-185186A and paragraphs 0024 to 0080 of JP2014-43010A. The thing can be illustrated.
  • the curable ink composition preferably contains 0.5 to 15% by mass of a photopolymerization initiator having a molecular weight of 1,000 or more as a polymerization initiator with respect to the total mass of the curable ink composition.
  • the content is more preferably 5 to 10% by mass, and particularly preferably 0.5 to 5% by mass. If it is the above embodiment, migration in the obtained printed matter can be suppressed.
  • the photopolymerization initiator having a molecular weight of 1,000 or more preferably has a molecular weight of 1,000 to 3,000. More preferably, it is ⁇ 2,500, and further preferably 1,000 to 2,000.
  • a photoinitiator with a molecular weight of 1,000 or more a thioxanthone compound, a maleimide compound, a benzophenone compound, or the like having a molecular weight of 1,000 or more is preferable.
  • Speedcure 7010 (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, manufactured by Lambson).
  • a compound having a molecular weight of 1,000 or more and having two or more maleimide structures in the molecule can also be suitably used as a photopolymerization initiator having a molecular weight of 1,000 or more.
  • the curable ink composition does not contain a photopolymerization initiator having a molecular weight of less than 1,000, or the content of the photopolymerization initiator having a molecular weight of less than 1,000 is the total mass of the curable ink composition.
  • it is preferably more than 0% by mass and 1% by mass or less, and does not contain a polymerization initiator having a molecular weight of less than 1,000, or the content of the polymerization initiator having a molecular weight of less than 1,000 is curable. More preferably, it is more than 0% by mass and not more than 1% by mass with respect to the total mass of the ink composition.
  • the content of the initiator is more preferably more than 0% by mass and 0.5% by mass or less with respect to the total mass of the curable ink composition, and does not contain a polymerization initiator having a molecular weight of less than 1,000. Is particularly preferred. If it is the said aspect, the migration of the product which generate
  • a compound having a molecular weight of 1,000 or more and having two or more maleimide structures in the molecule can be suitably used.
  • the compound having a molecular weight of 1,000 or more and having two or more maleimide structures in the molecule preferably has a poly (alkyleneoxy group) in the molecule from the viewpoint of the flexibility of the cured film.
  • the compound having a molecular weight of 1,000 or more and having two or more maleimide structures in the molecule is preferably a compound represented by the following formula B-1.
  • L B1 represents a divalent linking group
  • X B1 represents an ether bond (—O—), an ester bond (— (C ⁇ O) —O—) or a carbonate bond
  • Q B1 represents A single bond or an alkylene group is represented
  • m represents an integer of 1 or more
  • n represents an integer of 2 or more
  • Z B1 represents an n-valent linking group.
  • L B1 is a single bond, a linear or branched alkylene group, an ether bond (—O—), an ester bond (— (C ⁇ O) —O. -), A carbonyl group, or a group in which two or more of these are combined is preferable, and a group in which an ester bond and an alkylene group are bonded is more preferable.
  • the group in which the ester bond and the alkylene group are bonded is preferably a group represented by the following formula B-1-2.
  • R B2 is an alkylene group having 1 to 4 carbon atoms, preferably a methylene group.
  • Wavy line portion represents a bonding position with X B1, * moiety represents a bonding position to the nitrogen atom in the maleimide structure.
  • Q B1 is preferably a linear or branched alkylene group having 1 to 6 carbon atoms.
  • X B1 is preferably an ether bond (—O—).
  • Z B1 represents an n-valent aliphatic group, an ether bond (—O—), an ester bond (— (C ⁇ O) —O—), An amino group and an n-valent linking group obtained by combining two or more of these are preferable.
  • n is preferably an integer of 2 to 6, and more preferably an integer of 2 to 4.
  • the molecular weight of the compound having a molecular weight of 1,000 or more and having two or more maleimide structures in the molecule is preferably 1,000 to 5,000.
  • Examples of the compound having a molecular weight of 1,000 or more and having two or more maleimide structures in the molecule include the following compounds.
  • a method for producing a compound having a molecular weight of 1,000 or more and having two or more maleimide structures in the molecule for example, by esterifying a maleimide carboxylic acid produced by a known method and a polyhydric alcohol compound. The method of obtaining is mentioned.
  • the manufacturing method of the said maleimide carboxylic acid the method of making it dry after making maleic anhydride and glycine react in acetic acid is mentioned.
  • the compound having a molecular weight of 1,000 or more and having two or more maleimide structures in the molecule commercially available compounds may be used.
  • BMI1500 and BMI3000 above, Designer Molecules, Inc.
  • Aronix UVT-302 manufactured by Toagosei Co., Ltd. is preferred.
  • the curable ink composition uses a compound that functions as a sensitizer (hereinafter also simply referred to as “sensitizer”) in order to absorb ultraviolet rays and promote decomposition of the polymerization initiator as a polymerization initiator. You may contain.
  • sensitizer a compound that functions as a sensitizer
  • the sensitizer examples include polynuclear aromatics (eg, pyrene, perylene, triphenylene, 2-ethyl-9,10-dimethoxyanthracene, etc.), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, Rose Bengal etc.), cyanines (eg thiacarbocyanine, oxacarbocyanine etc.), merocyanines (eg merocyanine, carbomerocyanine etc.), thiazines (eg thionine, methylene blue, toluidine blue etc.), acridines (eg , Acridine orange, chloroflavin, acriflavine, etc.), anthraquinones (eg, anthraquinone, etc.), squaliums (eg, squalium), coumarins (eg, 7-diethylamino-4-methylcoumarin
  • a polymerization initiator may be used individually by 1 type, or may use 2 or more types together.
  • the content of the polymerization initiator is preferably 1.0 to 15% by mass, more preferably 1.5 to 10% by mass, and preferably 2.0 to 10% by mass with respect to the total mass of the curable ink composition.
  • the content is more preferably 8.0% by mass, and particularly preferably 2.0 to 5.0% by mass. It is excellent in curability as it is the said range.
  • the curable ink composition used in the present invention can contain a colorant.
  • the colorant is not particularly limited and includes known pigments and dyes. From the viewpoint of weather resistance, color reproducibility, and stability to electron beams, pigments and / or oil-soluble dyes are preferable. Is more preferable.
  • As the colorant it is preferable to select a compound that does not function as a polymerization inhibitor from the viewpoint of not reducing the sensitivity of the curing reaction by active energy rays.
  • a pigment which can be used for this invention For example, the organic or inorganic pigment of the following number described in a color index can be used.
  • red or magenta pigments examples include Pigment Red 3, 5, 19, 22, 31, 38, 42, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53. : 1, 57: 1, 57: 2, 57: 3, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122 , 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 202, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37 , 50, 88, Pigment Orange 13, 16, 20, 36, and blue or cyan pigments include Pigment Blue 1,15, 15: 1, 15: 2, 15: 3, 15: 4.
  • Pigment Green 7, 26, 36, 50 as a green pigment
  • the pigment is appropriately dispersed in the ink composition after being added to the ink composition.
  • a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, or a paint shaker can be used.
  • the pigment may be directly added together with each component when preparing the ink composition. Further, in order to improve dispersibility, it may be added to a dispersion medium such as a solvent or a polymerizable compound used in the present invention in advance and uniformly dispersed or dissolved, and then blended.
  • a dispersion medium such as a solvent or a polymerizable compound used in the present invention in advance and uniformly dispersed or dissolved, and then blended.
  • the pigment in order to avoid deterioration of solvent resistance when the solvent remains in the cured image and the problem of VOC (Volatile Organic Compound) of the remaining solvent, the pigment is a polymerizable compound. It is preferable to add and mix in advance in such a dispersion medium. In consideration of only dispersibility, it is preferable to select a monomer having a low viscosity as the polymerizable compound used for adding the pigment.
  • One or more pigments may be appropriately selected and used according to the purpose of use of the ink composition.
  • the average particle size of the pigment particles is preferably 0.005 to 0.5 ⁇ m, more preferably 0.01 to 0.45 ⁇ m, and further It is preferable to select a pigment, a dispersant, a dispersion medium, a dispersion condition, and a filtration condition so that the thickness is preferably 0.015 to 0.4 ⁇ m.
  • This particle size control is preferable because clogging of the head nozzle can be suppressed and the storage stability, transparency, and curing sensitivity of the ink composition can be maintained.
  • the content of the colorant in the ink composition is appropriately selected depending on the color and purpose of use, but is preferably 0.01 to 30% by mass with respect to the mass of the entire ink composition.
  • the curable ink composition may contain a dispersant.
  • a dispersant for dispersing the colorant.
  • a polymer dispersant is preferable.
  • the “polymer dispersing agent” in the present invention means a dispersing agent having a weight average molecular weight of 1,000 or more.
  • Polymer dispersing agents include DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-111, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-166, , DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-182 (manufactured by BYK Chemie); , EFKA7462, EFKA7500, EFKA7570, EFKA7575, EFKA7580 (manufactured by Fuka Additive); Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (Sannopco); 5000, 9000, 12000, 13240, 13940, 17000, 22000,
  • a dispersing agent may be used individually by 1 type, or may use 2 or more types together.
  • the content of the dispersant is appropriately selected depending on the purpose of use, but is preferably 0.05 to 15% by mass with respect to the total mass of the curable ink composition.
  • a surfactant may be added to the curable ink composition in order to impart stable ejection properties for a long time.
  • the surfactant include those described in JP-A Nos. 62-173463 and 62-183457.
  • anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks
  • Nonionic surfactants such as copolymers
  • cationic surfactants such as alkylamine salts and quaternary ammonium salts.
  • a fluorine-type surfactant for example, organic fluoro compound etc.
  • silicone type surfactant for example, polysiloxane compound etc.
  • the organic fluoro compound is preferably hydrophobic.
  • examples of the organic fluoro compound include fluorine surfactants, oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin). No. (columns 8 to 17) and those described in JP-A Nos. 62-135826.
  • the polysiloxane compound is preferably a modified polysiloxane compound in which an organic group is introduced into a part of the methyl group of dimethylpolysiloxane.
  • modification include polyether modification, methylstyrene modification, alcohol modification, alkyl modification, aralkyl modification, fatty acid ester modification, epoxy modification, amine modification, amino modification, mercapto modification, etc. is not. These modification methods may be used in combination. Of these, polyether-modified polysiloxane compounds are preferred from the viewpoint of improving ejection stability in inkjet.
  • polyether-modified polysiloxane compound examples include, for example, SILWET L-7604, SILWET L-7607N, SILWET FZ-2104, SILWET FZ-2161 (manufactured by Nihon Unicar Co., Ltd.), BYK306, BYK307, BYK331, BYK333, BYK347. BYK348, etc.
  • KF-6020, X-22-6191, X-22-4515, KF-6011, KF-6012, KF-6015, and KF-6017 are preferably used as the surfactant.
  • Surfactant may be used individually by 1 type, or may use 2 or more types together.
  • the content of the surfactant is appropriately selected depending on the purpose of use, but is preferably 0.0001 to 5% by mass, and preferably 0.001 to 2% by mass with respect to the total mass of the curable ink composition. It is more preferable.
  • the curable ink composition may contain a polymerization inhibitor from the viewpoints of storage stability and suppression of head clogging.
  • the polymerization inhibitor include nitroso polymerization inhibitors, hindered amine polymerization inhibitors, hindered phenol polymerization inhibitors, hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, and cuperon Al. Of these, hindered phenol polymerization inhibitors are preferred.
  • a polymerization inhibitor may be used individually by 1 type, or may use 2 or more types together.
  • the content of the polymerization inhibitor is preferably 0.001 to 2% by mass, more preferably 0.01 to 1% by mass, and more preferably 0.02 to 2% by mass with respect to the total mass of the curable ink composition. It is especially preferable that it is 0.8 mass%.
  • the curable ink composition may contain a co-sensitizer, an ultraviolet absorber, an antioxidant, an anti-fading agent, a conductive salt, a solvent, a polymer compound, a basic compound, etc., as necessary, in addition to the above components. May be included.
  • known components can be used, for example, those described in JP-A-2009-22214.
  • a curable ink composition having a viscosity at 25 ° C. of 40 mPa ⁇ s or less in consideration of dischargeability. More preferably, it is 5 to 40 mPa ⁇ s, and further preferably 7 to 30 mPa ⁇ s.
  • the viscosity at the discharge temperature (preferably 25 to 80 ° C., more preferably 25 to 50 ° C.) is preferably 3 to 15 mPa ⁇ s, and more preferably 3 to 13 mPa ⁇ s. It is preferable that the composition ratio of the curable ink composition is appropriately adjusted so that the viscosity is in the above range.
  • the viscosity in the present invention is measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
  • the surface tension of the curable ink composition at 25 ° C. is preferably 20 mN / m or more and 40 mN / m or less, more preferably 20.5 mN / m or more and 35.0 mN / m or less, and 21 mN / m or more. It is more preferably 30.0 mN / m or less, particularly preferably 21.5 mN / m or more and 28.0 mN / m or less. When the content is in the above range, a printed matter excellent in blocking inhibition can be obtained.
  • a well-known method can be used as a measuring method of the surface tension at 25 degreeC in this invention, It is preferable to measure by the suspension ring method or the Wilhelmy method.
  • a method of measuring using an automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. or a method of measuring using SIGMA 702 manufactured by KSV INSTRUMENTS LTD is preferred.
  • the curable composition for undercoat (undercoat composition) used for forming the undercoat layer preferably contains a compound having an isocyanate group, a polymerizable compound, and a polymerization initiator.
  • the undercoat composition used in the present invention is an oily liquid composition curable by an electron beam, and is preferably an oily liquid composition curable by an ultraviolet ray and an electron beam.
  • Preferred embodiments of the polymerizable compound and the polymerization initiator used in the undercoat composition are the same as the preferred embodiments of the polymerizable compound and the polymerization initiator used in the curable ink composition.
  • the undercoat composition preferably contains 70% by mass or more of the polyfunctional polymerizable compound with respect to the total content of the polymerizable compound. Within the above range, the amount of residual monomer in the obtained printed matter can be further reduced.
  • the content of the polymerizable compound in the undercoat composition is preferably 5 to 95% by mass with respect to the total mass of the undercoat composition, from the viewpoint of compatibility between adhesion and blocking inhibition, and is preferably 5 to 50% by mass. It is preferably 10 to 40% by mass.
  • the content of the polymerization initiator is preferably 1.0 to 15% by mass, more preferably 1.5 to 10% by mass, and more preferably 2.0 to 8.% by mass with respect to the total mass of the undercoat composition.
  • the content is more preferably 0% by mass, and particularly preferably 2.0 to 5.0% by mass. It is excellent in curability as it is the said range.
  • the undercoat composition preferably contains a compound having an isocyanate group. It does not specifically limit as a compound which has an isocyanate group used for undercoat composition, A well-known isocyanate compound can be used.
  • the compound having an isocyanate group may be either aliphatic or aromatic isocyanate, but aliphatic isocyanate is preferred from the viewpoint of safety and stability.
  • the product marketed can also be used as a compound which has an isocyanate group.
  • Takenate series such as Takenate D103H, D204, D160N, D170N, D165N, D178NL, D110N (Mitsui Chemicals), Coronate HX, HXR, HXL, HXLV, HK, HK-T, HL, 2096 (Japan) Polyurethane Industry Co., Ltd.) is preferable.
  • TM-550 and CAT-RT-37-2K manufactured by Toyo Morton Co., Ltd.
  • X series solvent-free adhesives such as XC233-2 and XA126-1 (manufactured by Dainichi Seika Kogyo Co., Ltd.)
  • the commercial item of the 2 liquid mixing type adhesive agent of an isocyanate compound and the polyol compound mentioned later can also be used.
  • the compound which has an isocyanate group may be used individually by 1 type, or may use 2 or more types together.
  • the content of the compound having an isocyanate group is preferably 2 to 90% by mass, more preferably 5 to 80% by mass, and still more preferably 10 to 75% by mass with respect to the total mass of the undercoat composition. .
  • the undercoat composition may contain a polyol compound.
  • a polyol compound As the polyol compound, a diol compound is preferable.
  • the polyol compound is not particularly limited, but when the isocyanate compound is TM-550, CAT-RT-37-2K (manufactured by Toyo Morton Co., Ltd.), and when the isocyanate compound is XC233-2, It is possible to use products that are commercially available as two-component mixed adhesives of isocyanate compounds and polyol compounds, such as X series useless adhesives (manufactured by Dainichi Seika Kogyo Co., Ltd.) such as XA126-1. .
  • a polyol compound may be used individually by 1 type, or may use 2 or more types together.
  • the content of the polyol compound is preferably 5 to 50% by mass with respect to the total mass of the undercoating composition, and is 10 to 40% by mass. It is more preferable.
  • the primer composition may include a binder polymer.
  • a binder polymer an inactive resin having no polymerizable group is preferable.
  • known binder polymers such as polyester resins, polyurethane resins, vinyl resins, acrylic resins, rubber resins can be used, but acrylic resins are preferable, and inert methyl methacrylate homopolymer and / or copolymer. A polymer is more preferred.
  • polymethyl methacrylate manufactured by Aldrich (molecular weight 10,000, catalog number 81497; molecular weight 20,000, catalog number 81498; molecular weight 50,000, catalog number 81501), methyl methacrylate / n-butyl methacrylate copolymer (mass 85/15, molecular weight 75,000; catalog number 474029), etc .
  • ELVACITE 2013 methyl methacrylate / n-butyl methacrylate copolymer, mass ratio 36/64, molecular weight 37,000), 2021, 614, manufactured by Lucite International 4025, 4026, 4028, etc .
  • the weight average molecular weight (Mw) of the binder polymer is preferably 1,000 or more, more preferably 1,000 to 1,000,000, and still more preferably 5,000 to 200,000. 8,000 to 100,000 is particularly preferable.
  • a binder polymer may be used individually by 1 type, or may use 2 or more types together.
  • the content of the binder polymer is preferably 0.2 to 15% by mass and more preferably 1 to 10% by mass with respect to the total mass of the undercoat composition. When the content of the binder polymer is within the above range, a printed matter excellent in blocking inhibition can be obtained.
  • the undercoat composition that can be used in the present invention may contain a colorant, but preferably contains or does not contain a white colorant, and more preferably does not contain it.
  • a white colorant a white pigment is preferable.
  • the white pigment Pigment White 6, 18, 21 or the like can be used depending on the purpose.
  • the undercoat composition contains a colorant, the content of the colorant is appropriately selected depending on the color and intended use, but is 0.01 to 30% by mass with respect to the total mass of the undercoat composition. It is preferable.
  • the undercoat composition used in the present invention may contain a dispersant, a surfactant, a polymerization inhibitor, and other components.
  • a dispersant, surfactant, polymerization inhibitor, and other components used in the undercoat composition the dispersant, surfactant, polymerization inhibitor, and other components in the curable ink composition described above are used. It can be used suitably, and a preferable aspect is the same.
  • the viscosity at 25 ° C. of the undercoat composition is preferably 40 mPa ⁇ s or less, preferably 5 to 40 mPa ⁇ s, and more preferably 7 in consideration of dischargeability. ⁇ 30 mPa ⁇ s.
  • the viscosity at the discharge temperature (preferably 25 to 80 ° C., more preferably 25 to 50 ° C.) is preferably 3 to 15 mPa ⁇ s, and more preferably 3 to 13 mPa ⁇ s. It is preferable to adjust the composition ratio of the undercoat composition appropriately so that the viscosity falls within the above range.
  • the surface tension of the undercoat composition at 25 ° C. is preferably 15 mN / m to 40 mN / m, more preferably 20 mN / m to 35 mN / m, and further preferably 20 mN / m to 30 mN / m. preferable.
  • the undercoating composition can be prepared by stirring and mixing the components.
  • all the components contained in the undercoat composition may be stirred and mixed at the same time, or the composition obtained by stirring and mixing the components other than the isocyanate compound and / or the radical polymerization initiator is stored.
  • an undercoat composition may be prepared by adding an isocyanate compound and / or a radical polymerization initiator before use.
  • the undercoat composition is preferably applied to the recording medium within one day after preparation from the viewpoint of applicability.
  • the printed matter of the present invention is a printed matter in which a cured film is formed by the cured film forming method of the present invention.
  • the inkjet image recording method using the cured film forming method of the present invention is preferable because it can provide a printed material that has excellent adhesion to a substrate, a small amount of residual monomer, and excellent image quality.
  • the printed matter of this invention has an adhesive layer and a laminate film in this order on the printed matter obtained by the cured film formation method of this invention.
  • the adhesive layer and the laminate film are synonymous with the adhesive layer and the laminate film described in the laminating step, and the preferred embodiments are also the same.
  • magenta pigment dispersion 300 parts by mass of IRGALITE RED D3773, 1050 parts by mass of SR341, and 150 parts by mass of EFKA7701 were mixed with stirring to obtain a magenta pigment dispersion.
  • the magenta pigment dispersion was prepared in a disperser Motor Mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.
  • Examples 1 to 14 and Comparative Examples 1 to 3 ⁇ Image forming method>
  • CA3 heads manufactured by TOSHIBA TEC CO., LTD. Were arranged in parallel for each color. The head was heated to 45 ° C., and the frequency was controlled so that drawing could be performed with a droplet ejection size of 42 pl.
  • the LED light source an LED light source unit having peak wavelengths of 385 nm and 300 nm was used.
  • OPP biaxially oriented polypropylene, thickness 25 ⁇ m
  • the recording medium was scanned at a speed of 50 m / min, and the ink composition was discharged onto the recording medium.
  • the ink composition was made into a semi-cured state using the first active energy ray source (accumulated exposure amount 50 mJ / cm 2 ) described in Table 2. Thereafter, the ink composition was cured using a second active energy ray source described in Table 2. In this way, a print was obtained.
  • the electron beam irradiation apparatus CB250 (manufactured by Iwasaki Electric Co., Ltd.) was used, and the acceleration voltage and absorbed dose were as shown in Table 2.
  • the LED light source had an integrated exposure amount of 100 mJ / cm 2 and a peak wavelength as shown in Table 2.
  • nitrogen was purged so that the oxygen concentration was 300 ppm or less.
  • a solid image was formed in the area of 10 cm square with a thickness of 24 ⁇ m by the above image forming method to obtain an image sample.
  • a 1 cm wide cello tape (registered trademark) was applied to the image surface of the obtained image sample in a length of 5 cm, and then peeled off. The peeled cellotape (registered trademark) was visually observed.
  • B Coloring is slightly observed on the cello tape (registered trademark) (the area is 1 mm 2 or less).
  • C Coloring is observed on the cello tape (registered trademark).
  • ⁇ Image quality evaluation> The quality of the line (line) in the nozzle arrangement direction of the head and the line (line) in the vertical direction in the image was evaluated according to the following evaluation criteria. Specifically, it was evaluated by measuring the number of spots that can be visually discerned in a line length of 2.54 cm. A: Bleed is not seen and the line quality is good. B: There are 2 or less spots. C: There are 3 or more spots.
  • Examples 12 to 14 a curable ink composition having a maleimide polymerization initiator is used, but by using an active energy ray source having a wavelength of 310 nm or less as the first active energy ray source, the image quality is excellent. And reducing the amount of residual monomer.
  • Undercoat composition 1 Takenate D170N 70 parts by mass, SR341 25 parts by mass, Speedcure 7010 4 parts by mass, BYK-307 1 part by mass, using a mixer (Silverson L4R) at 5,000 rpm at room temperature (25 ° C.) Undercoat composition 1 was prepared by stirring and mixing at 20 minutes per minute.
  • Undercoat composition 2 10 parts by weight of SR444, 59.8 parts by weight of SR341, 15 parts by weight of Takenate D170N, 10 parts by weight of polyester resin LTH, 4 parts by weight of IRGACURE819, 1 part by weight of BYK-307, mixer (Silverson) Undercoat composition 2 was prepared by stirring and mixing at room temperature (25 ° C.) for 20 minutes at 5,000 rpm.
  • Example 15 In Example 15, the ink jet recording apparatus shown in FIG. 1 was used. In this ink jet recording apparatus, an undercoat liquid application roller and an LED light source having a peak wavelength of 385 nm are provided in front of an ink jet head. As the recording medium, polyethylene terephthalate (PET, thickness 12 ⁇ m) was used. The recording medium is scanned at a speed of 50 m / min to give an undercoat composition, and then the LED light source (integrated exposure 50 mJ / cm 2 ) is used as the first energy ray source to semi-cure the undercoat composition. It was in a state.
  • PET polyethylene terephthalate
  • Example 16 (Examples 16 and 18 to 21, and Comparative Example 4)
  • an LED light source ( A step of making the ink composition semi-cured using an integrated exposure amount of 50 mJ / cm 2 ) was added.
  • a printed matter of Example 16 was obtained.
  • Examples 18 to 21 and Comparative Example 4 a printed matter was obtained in the same manner as the procedure of the image forming method of Example 16 except that the acceleration voltage of the electron beam or the absorbed dose in the electron beam irradiation was changed.
  • Example 17 In Example 17, a printed matter was obtained in the same manner as in the procedure of the image forming method of Example 16 except that the undercoat composition was not applied and the first active energy ray source was not used. . This printed matter was evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 3.
  • Example 22 In the same manner as the magenta pigment dispersion, a pigment dispersion (yellow), a pigment dispersion (cyan), a pigment dispersion (black), and a pigment dispersion (white) were prepared under the composition and dispersion conditions shown in Table 4.
  • Table 4 the column labeled “-” indicates that the corresponding compound is not contained.
  • Ink compositions 10 to 13 were prepared so that the compositions shown in Table 5 were obtained. Using ink compositions 1 and 10 to 13, full-color images were produced under the same conditions as in Example 16, and evaluated in the same manner as in Example 1. Evaluation results for adhesion, image quality, and residual monomer amount equivalent to those of Example 16 were obtained.
  • 12 Recording medium
  • 14 Undercoat composition application roller
  • 17 Active energy ray source for undercoat composition semi-curing
  • 18K, 18C, 18M, 18Y, 18W Inkjet head
  • 20K, 20C, 20M, 20Y For semi-curing Active energy ray source
  • 22 nitrogen purge electron beam irradiation unit
  • 24 delivery roller
  • 26 take-up roller
  • 28 nip roll

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Abstract

L'invention concerne : un procédé de formation de film durci apte à former un film durci qui présente une excellente adhésion au substrat et présente une teneur réduite en monomères résiduels ; un procédé d'enregistrement d'une image par jet d'encre d'une excellente qualité d'image à l'aide du procédé de formation de film durci ; et une matière imprimée. Le procédé de formation de film durci comprend une étape d'administration d'une composition dans laquelle une composition durcissable contenant un composé polymérisable est délivrée à une surface d'un support d'enregistrement et une étape d'irradiation dans laquelle la composition durcissable est irradiée avec au moins deux types de rayons actiniques. En tant qu'au moins une partie des rayons actiniques de l'étape d'irradiation, des faisceaux d'électrons produits avec une tension d'accélération inférieure ou égale à 130 kV sont utilisés. Lors de l'étape d'irradiation, une irradiation avec les faisceaux d'électrons est réalisée de telle sorte qu'il en résulte une dose absorbée de 20 à 75 kGy.
PCT/JP2016/056895 2015-03-31 2016-03-04 Procédé de formation de film durci, procédé d'enregistrement d'image par jet d'encre, et matière imprimée WO2016158209A1 (fr)

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WO2018207487A1 (fr) * 2017-05-12 2018-11-15 コニカミノルタ株式会社 Procédé de formation d'image
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JP7184744B2 (ja) * 2019-12-27 2022-12-06 富士フイルム株式会社 インクセット及び画像記録方法
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JP2022168697A (ja) 2021-04-26 2022-11-08 サカタインクス株式会社 電子線硬化型印刷インキ組成物及び電子線硬化型印刷インキ組成物を印刷して得られた印刷物
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WO2021229974A1 (fr) * 2020-05-13 2021-11-18 富士フイルム株式会社 Ensemble d'encres, procédé d'impression d'image, et imprimé
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WO2023181502A1 (fr) * 2022-03-23 2023-09-28 富士フイルム株式会社 Procédé d'impression d'image

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