Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
  • B41M3/008—Sequential or multiple printing, e.g. on previously printed background; Mirror printing; Recto-verso printing; using a combination of different printing techniques; Printing of patterns visible in reflection and by transparency; by superposing printed artifacts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M1/00—Inking and printing with a printer's forme
  • B41M1/02—Letterpress printing, e.g. book printing
  • B41M1/04—Flexographic printing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M1/00—Inking and printing with a printer's forme
  • B41M1/06—Lithographic printing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M1/00—Inking and printing with a printer's forme
  • B41M1/14—Multicolour printing
  • B41M1/18—Printing one ink over another
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M1/00—Inking and printing with a printer's forme
  • B41M1/26—Printing on other surfaces than ordinary paper
  • B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
  • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
  • B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/12—Printing inks based on waxes or bitumen

Definitions

• the present invention relates to a method for manufacturing printed matter.
• laminates made by combining various films such as polyolefin, polyester, and polyamide are used as packaging materials according to the functionality required after bag making, such as strength and heat resistance.
• packaging materials due to growing environmental awareness, there is a demand for recyclability of packaging materials, and monomaterials composed only of the same type of film material are attracting attention.
• the printed image after bag making is visible from the back side of the base material, it is reverse printing, in which a mirror image is printed on the base film.
• reverse printing since lamination is always performed after printing, the aging process after lamination cannot be omitted, and it is not possible to move to the processing and filling process immediately after printing.
• Gravure printing which is currently the mainstream of flexible packaging printing, can produce printed matter that looks vivid, but because it uses ink that contains a large amount of solvent, it requires a large amount of energy to dry the ink solvent and exhaust air. is required, and the environmental load is also large.
• different inks are used for reverse side printing and front side printing, which are adjusted to film strength and lamination suitability according to the characteristics of each, so they cannot be used in common.
• Patent Document 3 a printing process is disclosed that imparts wet-on-wet printability to active energy ray-curable flexographic ink. According to this, after printing the pre-printed active energy ray-curable flexo ink on the film, it is dried to make it into a gel state, and the post-printed active energy ray-curable flexo ink is printed to maintain good trapping properties. , colors are applied repeatedly, and finally cured by EB irradiation.
• the ink contains a solvent that can be removed. Fluctuations in ink physical properties occur. As a result, the density of process colors tends to fluctuate, and there are problems with continuous printing stability, such as lack of stability in density and halftone dot shape during continuous printing, and large variations in density within the same print surface. rice field.
• the present invention includes an ink (A) transfer step of transferring colorless or white ink (A) defined below to a substrate, and a drying step of evaporating water or a solvent contained in the ink (A). , an ink (B) transfer step of transferring the ink (B) defined below to a substrate, and an irradiation step of irradiating the transferred ink with an active energy ray, in this order.
• the printed matter manufacturing method of the present invention it is possible to perform surface printing with excellent wet-on-wet printability and density stability.
• the printed matter obtained exhibits excellent hiding power and abrasion resistance.
• the present invention includes an ink (A) transfer step of transferring colorless or white ink (A) defined below to a substrate, a drying step of evaporating water or a solvent contained in the ink (A), The ink (B) transfer step of transferring the ink (B) defined below to the base material, and the irradiation step of irradiating the transferred ink with an active energy ray are included in this order.
• white ink or colorless anchor ink which is printed on almost the entire surface of the base material and serves as the base color of the printed image, is used to improve the concealability (in the case of white ink) and gloss of the appearance of the printed matter. liquidity is important.
• the ink contains a solvent that can be removed, and the ink is dried between cylinders so that it can be peeled off in post-printing, preventing color mixing and realizing wet-on-wet printability.
• each ink contains a solvent that can be distilled off, the physical properties of the ink change due to solvent volatilization during storage and in a printing machine, in addition to drying.
• White which is the base color, generally produces solid images, requires a large amount of ink supply, and requires high density. It is desirable that the variation is small during continuous printing because it affects the printing quality such as the dot shape and the shape of the halftone dot.
• the white or colorless ink which is the base color, contains volatile water or a solvent to make it highly fluid
• the post-printing is performed by providing a drying process before the post-printing. is stripped off and suppresses color mixing.
• color inks such as process colors and special colors for post-printing do not substantially contain volatile components, so the ink physical properties such as viscosity are less variable, and the ink supply amount is less likely to fluctuate during continuous printing. Improve the stability of print quality.
• active energy ray-curable ink A preferred embodiment of the active energy ray-curable ink, which is common to the ink (A) and the ink (B), will be described.
• the active energy ray-curable ink in the present invention that is, the ink (A) and/or the ink (B) preferably contains a (meth)acrylate having an alicyclic skeleton.
• a (meth)acrylate having an alicyclic skeleton By including a (meth)acrylate having an alicyclic skeleton, the volume shrinkage during curing by irradiation with active energy rays is reduced, and the adhesiveness of the cured ink film to the substrate is improved.
• Examples of (meth)acrylates having an alicyclic skeleton include isobornyl (meth)acrylate, norbornyl (meth)acrylate, norbornane-2-methanol (meth)acrylate, cyclohexyl (meth)acrylate, 1-adamantyl (meth)acrylate, 3-methyladamantan-2-yl (meth)acrylate, 3-ethyladamantan-2-yl (meth)acrylate, 9,9-bis[4-(meth)acryloyloxyethoxyphenyl]fluorene, 9,9-bis[ 4-(3-(meth)acryloyloxy-2-hydroxypropyloxy)phenyl]fluorene, tricyclopentenyl (meth)acrylate, tricyclopentenyloxy (meth)acrylate, tricyclodecane monomethylol (meth)acrylate, dicyclo pentadiene cyclodecanedimethanol di(meth)acrylate and the like.
• the alicyclic skeleton is selected from a norbornane skeleton, an adamantane skeleton, a tricyclodecane skeleton, and a dicyclopentadiene skeleton, since the volume shrinkage during curing is small and the physical properties of the cured film, such as scratch resistance, are good. more preferably any one or more.
• a monofunctional or polyfunctional (meth)acrylate that does not have an alicyclic skeleton can also be used.
• Examples of monofunctional (meth)acrylates include hexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, benzyl (Meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, polyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, N-(2-hydroxyethyl)acrylamide , N-(2-hydroxyethyl)methacrylamide, N-(2-hydroxymethyl)acrylamide, N-(2-hydroxymethyl)methacrylamide, acryloylmorpholine, dimethylacrylamide, methoxymethylacrylamide, diethylacrylamide, and isopropylacrylamide. be done.
• bifunctional (meth)acrylates include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,3-butylene glycol.
• trifunctional (meth)acrylates examples include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, isocyanuric acid tri(meth)acrylate. ) acrylates, their ethylene oxide adducts, propylene oxide adducts, and the like.
• tetrafunctional (meth)acrylates include pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, diglycerin tetra(meth)acrylate, and their ethylene oxide adducts and propylene oxide adducts. be done.
• penta- or higher-functional (meth)acrylates examples include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide adducts and propylene oxide adducts thereof.
• the active energy ray-curable ink in the present invention that is, the ink (A) and/or the ink (B) preferably contains a resin.
• the resins include acrylic resins, urethane resins, phthalate resins, and the like, and commercially available products may be used, or synthetic products may be used.
• the acrylic resin can be obtained by polymerizing a (meth)acrylate monomer alone or by mixing two or more of them in an organic solvent in the presence of a polymerization initiator. It can also be obtained by copolymerizing styrene, ⁇ -methyl-styrene, or the like.
• acrylic resins examples include the "Hirosu” (registered trademark) series manufactured by Seiko PMC.
• the urethane resin can be obtained by mixing one or more types of polyol and polyisocyanate, and performing a polycondensation reaction in an organic solvent in the presence of a condensing agent.
• polyols include polyester polyols, polycarbonate polyols and polyether polyols
• polyisocyanates include polyurethane polyisocyanates and isocyanurates.
• the phthalate resin can be obtained by polymerizing diallyl orthophthalate or diallyl isophthalate alone or by mixing two of them in an organic solvent in the presence of a polymerization initiator.
• phthalate resins examples include the "Daisodap” (registered trademark) series manufactured by Osaka Soda Co., Ltd. and "Daiso Isodap” (registered trademark).
• pigments contained in the active energy ray-curable ink of the present invention include phthalocyanine-based pigments, soluble azo-based pigments, insoluble azo-based pigments, lake pigments, quinacridone-based pigments, isoindoline-based pigments, threne-based pigments, and metal complex-based pigments.
• Colorless extender pigments such as mica (hydrated aluminum potassium silicate) and talc (magnesium silicate) can also be used. Alternatively, it can be an overprint varnish.
• the active energy ray-curable ink in the present invention that is, the ink (A) and/or the ink (B) preferably contains wax.
• the active energy ray-curable ink contains wax, the scratch resistance and slipperiness of the cured film are improved.
• wax natural waxes such as carnauba wax, Japan wax, montan wax and lanolin, hydrocarbon waxes, polytetrafluoroethylene waxes, polyamide waxes, and synthetic waxes such as silicone compounds can be used. Of these, hydrocarbon waxes are preferred because of their excellent scratch resistance.
• hydrocarbon waxes examples include Fischer-Tropsch wax, polyethylene wax, polypropylene wax, paraffin wax, and microcrystalline wax. These waxes can be used singly or in combination of two or more.
• the content of the wax in ink (A) or ink (B) is preferably 0.1% by mass or more and 10% by mass or less.
• the content of the wax is 0.1% by mass or more, preferably 0.5% by mass or more, and even more preferably 1% by mass or more, the scratch resistance and slipperiness are improved.
• the content of the wax is 10% by mass or less, preferably 5% by mass or less, and even more preferably 3% by mass or less, the wax is well dispersed and fluidity is improved.
• the active energy ray-curable ink in the present invention that is, the ink (A) and/or the ink (B) contains other additives such as photopolymerization initiators, pigment dispersants, antifoaming agents, leveling agents, and the like. It may contain additives.
• the active energy ray-curable ink in the present invention may be an ultraviolet-curable ink containing a photopolymerization initiator, but radiation-curable ink containing no photopolymerization initiator is preferred from the viewpoint of reducing environmental burden. more preferred.
• Both flexographic ink and offset ink can be used as the active energy ray-curable ink in the present invention.
• As the offset ink an ink for waterless planographic printing may be used.
• pigments and auxiliaries are added to resin varnish obtained by dissolving resins in monofunctional and polyfunctional (meth)acrylates, and in the case of offset ink, a three-roll mill is used.
• flexographic ink it can be synthesized by dispersing and mixing using an attritor, ball mill, sand mill, or the like.
• Ink (A) is a volatile active energy ray-curable ink containing water or a solvent.
• solvents in ink (A) include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, methyl ethyl ketone, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, propyl propionate, butyl propionate, Ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate and the like. You may use a solvent in combination of 1 type(s) or 2 or more types. A combination of water and a solvent may also be used.
• the ink (A) preferably contains water or a solvent with a boiling point of 150°C or less at 1 atm.
• the boiling point of water or solvent is 150° C. or lower, preferably 120° C. or lower, moderate quick-drying properties are imparted.
• the ink (B) for post-printing can be peeled off, and color mixture can be suppressed.
• the total content of water and/or solvent in the ink (A) is preferably 10% by mass or more and 50% by mass or less.
• the content is 10% by mass or more, more preferably 20% by mass or more, it is stripped off by ink (A) in post-printing after the drying process, thereby suppressing color mixing.
• the content is 50% by mass or less, more preferably 40% by mass or less, quick-drying property is imparted by the drying process.
• Ink (A) has a viscosity ⁇ A of 0.1 Pa s or more and 5 Pa s at 25 ° C. and a rotation speed of 0.5 rpm according to JIS Z8803:2011 "Method for measuring viscosity with a coaxial double cylindrical rotational viscometer". The following are preferable.
• ⁇ A is 0.1 Pa ⁇ s or more and 5 Pa ⁇ s or less, more preferably 0.5 Pa ⁇ s or more and 2 Pa ⁇ s or less, the fluidity of the ink that forms a colorless or white base color is improved.
• both flexographic ink and offset ink can be used, but the ink (A) is particularly flexographic ink which has a low viscosity and may contain water or a solvent. is preferably used.
• Examples of commercially available volatile electron beam curable flexographic inks include “Wetflex” manufactured by Sun Chemical and “Gelflex” manufactured by Sakata-Inx.
• Ink (B) is a non-volatile active energy ray-curable ink containing substantially no water or solvent. “Substantially free of water or solvent” means that the total content of water and solvent in the ink is 0.5% by mass or less.
• Ink (B) has a viscosity ⁇ B of 20 Pa s or more and 200 Pa s or less at 25° C. and a rotation speed of 0.5 rpm according to JIS Z8803:2011 “Method for measuring viscosity using a coaxial double cylindrical rotational viscometer”.
• ⁇ B is 20 Pa ⁇ s or more and 200 Pa ⁇ s or less, more preferably 40 Pa ⁇ s or more and 100 Pa ⁇ s or less, it is possible to suppress fluctuations in the physical properties of color inks such as process colors and special colors during printing.
• ⁇ A and ⁇ B are within their respective preferable ranges, because the tackiness of the inks can be balanced and the continuous printing stability can be improved.
• both flexographic ink and offset ink can be used.
• the ink (B) particularly, an offset ink having a high viscosity and containing no volatile components is used. is preferred.
• non-volatile electron beam curable offset inks examples include “Sun Beam” manufactured by Sun Chemical and “XCURA EVO” manufactured by Flint.
• the center drum type means that there is a single impression cylinder that sandwiches the printed material so as to face the cylinder for transferring the ink and the pressure cylinder.
• Center drum presses are suitable for wet-on-wet printing processes because they do not require guide rolls to transport the film between cylinders.
• center drum type printing presses include "MIRAFLEX” manufactured by Windmoeller & Hoelscher and “ONYX XS” manufactured by UTECO, which are commercially available as flexographic printing presses, and are commercially available as offset printing presses.
• MIRAFLEX manufactured by Windmoeller & Hoelscher
• ONYX XS manufactured by UTECO
• CI-8 manufactured by COMEXI can be mentioned.
• Base material In the method for producing a printed matter of the present invention, it is preferable to use a non-absorbent raw material such as metal or film as the base material.
• the film examples include polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyester such as polylactic acid, polyamide, polyimide, polyalkyl (meth)acrylate, polystyrene, poly ⁇ methylstyrene, polycarbonate, polyvinyl alcohol, polyvinyl acetal, and polyvinyl chloride.
• polyester such as polylactic acid, polyamide, polyimide, polyalkyl (meth)acrylate, polystyrene, poly ⁇ methylstyrene, polycarbonate, polyvinyl alcohol, polyvinyl acetal, and polyvinyl chloride.
• vinyl and polyvinylidene fluoride examples of the film.
• the film may be subjected to surface treatment such as burning treatment, easy-adhesion coating, and chemical vapor deposition.
• the thickness of the base material is preferably 5 ⁇ m or more and 50 ⁇ m or less.
• the thickness of the substrate is preferably 5 ⁇ m or more, preferably 10 ⁇ m or more.
• the mechanical strength of the substrate required for printing can be effectively obtained.
• the thickness is set to 50 ⁇ m or less, preferably 30 ⁇ m or less, the cost of the substrate can be kept low.
• the base material is coated paper such as art paper, coated paper, cast paper, non-coated paper such as woodfree paper, newsprint, Japanese paper, synthetic paper, aluminum metallized paper, etc.
• ink (A) Alternatively, transparent ink may be used instead of white ink.
• the form of the base material used in the method for producing printed matter of the present invention may be either sheet-like or roll-like.
• color printed matter requires a printing unit to transfer ink for the number of colors to be printed.
• the ink in the image area is transferred from the anilox roll or ink roll to the transfer surface of the printing material through a printing plate or, depending on the method, a blanket.
• flexographic printing for low-viscosity volatile ink and offset printing for high-viscosity non-volatile ink as a method of transferring ink to the surface to be printed.
• the printing method of the present invention includes an ink (A) transfer step of transferring colorless or white ink (A) to a substrate, and an ink (B) transfer step of transferring ink (B) to the substrate. ) including the transfer step in this order.
• surface printing can be achieved by first transferring the white ink (A) to the base material.
• the base material itself can separate the hardened ink layer from the packaging object even in flexible packaging for food and daily necessities, making it unnecessary to attach a sealant. .
• the water or solvent contained in the volatile ink that has been transferred to the substrate is removed by an air blower such as a hot air dryer generally used in flexo printing machines. can be done. If the volatile component is a compound containing a hydroxyl group such as water, an IR dryer can also be used.
• an air blower such as a hot air dryer generally used in flexo printing machines.
• an IR dryer can also be used.
• the viscosity of the volatile ink is within the range of ⁇ A described above and the viscosity of the non-volatile ink is within the range of ⁇ B described above
• the non-volatile ink which has overwhelmingly high viscosity, peels off and mixes colors, making normal printing impossible.
• by continuously printing non-volatile ink in post-printing through the drying process of the volatile ink of the present invention peeling off and color mixing due to ink in post-printing are suppressed, and continuous printing with stable quality is possible. It becomes possible.
• the active energy ray-curable overprint varnish is transferred to the substrate to which the ink (A) and the ink (B) have been transferred. It is preferable to include a step (overprint varnish transfer step).
• the active energy ray-curable overprint varnish plays a role in protecting the printed ink hardened product, and improves the scratch resistance of the surface printed product.
• the transferred ink is irradiated with active energy rays.
• active energy ray sources include ultraviolet rays (especially LED-UV), electron beams, gamma rays, and the like. Radiation such as electron beams and gamma rays generates high-energy secondary electrons in irradiated substances, excites surrounding molecules, and generates reactive species represented by radicals.
• the material to be irradiated is an active energy ray-curable ink, radicals are generated in the ink, radical polymerization proceeds, and a cured ink film is formed.
• the electron beam with a low acceleration voltage has sufficient permeability to the thickness of the ink film of 10 ⁇ m or less, is given the energy necessary for curing, and can be handled without special qualifications at the time of use. is preferably used because it is easy to
• the acceleration voltage of the electron beam is preferably 50 kV or higher, more preferably 90 kV or higher, and even more preferably 110 kV or higher, at which a sufficient dose penetrates the ink film. Further, as the depth of penetration increases, the dose applied to the inside of the film also increases.
• the higher the electron beam irradiation dose the greater the amount of radical species generated in the target substance and the greater the damage to the film.
• Ink viscosity ( ⁇ A , ⁇ B ) It was measured according to JIS Z8803:2011 "Viscosity measurement method using a coaxial double cylindrical rotational viscometer”. Cylinder spindle No. 4 was attached to a B-type viscometer (DV-II manufactured by BROOKFIELD), and measurement was performed under the measurement conditions of 25° C. and a rotation speed of 0.5 rpm.
• Tack value 1.3 ml of ink is applied to the roller of an Inkometer (“INKOGRAPH” TYPE-V manufactured by Tester Sangyo Co., Ltd.), and the roller is operated at a roller temperature of 38°C and a rotation speed of 400 rpm, and the tack value after 1 minute is measured. It was measured.
• Opacity Opacity was measured using a reflection densitometer (eXact advance, manufactured by xRite) on a portion of the printed matter that was solid white only. A value of 55% or more is good, and a value of 60% or more is very good.
• eXact advance manufactured by xRite
• Abrasion Resistance of Printed Matter A randomly selected area of 3 cm ⁇ 3 cm was rubbed back and forth with a human fingernail 20 times for a solid white portion of the printed matter, and evaluated according to the following criteria. A: No scratches due to nails were observed. B: Partial peeling of the ink was observed along the nail marks.
• ⁇ Print unit> As a printing unit corresponding to the 1st to 5th cylinders of the printing press described later, one of the following was used.
• Flexographic Printing Unit AWP DEW manufactured by Asahi Kasei was used as a printing plate, and a corresponding color image was exposed and developed to make a plate.
• Nova Gold manufactured by Praxair Surface Technologies was used as an anilox roller.
• Offset Printing Unit A waterless planographic printing original plate (TAC-VT4, manufactured by Toray Industries, Inc.) was used as a printing plate, and a corresponding color image was exposed and developed to make a plate.
• the rubber roller was 726-40 manufactured by Boetcher, and the blanket was T414W manufactured by Kinyo Co., Ltd.
• White ink was set on the 1st cylinder, black ink on the 2nd cylinder, cyan ink on the 3rd cylinder, magenta ink on the 4th cylinder, and yellow ink on the 5th cylinder in order from the upstream side of the running direction of the printing base material.
• an electron beam was irradiated with an acceleration voltage of 110 kV and an irradiation dose of 30 kGy to cure the ink and obtain a printed matter.
• Print method 1 In printing method 1, a flexographic printing unit was installed on the first cylinder of a printing machine (CI-8 manufactured by COMEXI), and an offset printing unit was installed on the second to fifth cylinders. Hot air drying was performed only between the first and second cylinders.
• Print method 2 In printing method 2, all the 1st to 5th cylinders of the printing machine (ONYX XS manufactured by UTECO) were used as flexographic printing units, and hot air drying was performed between the cylinders.
• Print method 3 In printing method 3, all the 1st to 5th cylinders of the printing machine (ONYX XS manufactured by UTECO) were used as flexographic printing units, and drying was not performed between the cylinders.
• Print method 4 In printing method 4, all the 1st to 5th cylinders of the printing machine (CI-8 manufactured by COMEXI) were used as offset printing units, and drying was not performed between the cylinders.
• Print method 5 In printing method 5, flexographic printing units were installed on the 1st and 8th cylinders of a printing machine (CI-8 manufactured by COMEXI), and offset printing units were used on the 2nd to 5th cylinders. Hot air drying was performed only between the first and second cylinders. An active energy ray-curable overprint varnish was set on the eighth cylinder.
• Monomer 1 pentaerythritol triacrylate (“Miramer” (registered trademark) M340 manufactured by MIWON)
• Monomer 2 trimethylolpropane triacrylate ethylene oxide adduct (“Miramer” (registered trademark) M3190 manufactured by MIWON)
• Monomer 3 (meth)acrylate having an alicyclic skeleton, tricyclodecanedimethanol diacrylate (“Miramer” (registered trademark) M262 manufactured by MIWON)
• Monomer 4 1,6-hexanediol diacrylate (“NK Ester” (registered trademark) A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).
• Oligomer Oligomer: urethane acrylate (UF-8001G manufactured by Kyoeisha Chemical Co., Ltd.).
• Acrylic resin 25% by mass of methyl methacrylate, 25% by mass of styrene, and 50% by mass of methacrylic acid. molecular weight 34,000, acid value 102 mgKOH/g).
• Polymerization inhibitor Polymerization inhibitor: p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.).
• Base material 1 PET film (S-46 manufactured by Polyplex, thickness 12 ⁇ m)
• Base material 2 PE film (PE3K-H manufactured by Futamura Chemical Co., Ltd., thickness 25 ⁇ m)
• Substrate 3 Biaxially oriented polypropylene (OPP) film (“AlOx-Lyte” manufactured by Jindal Film, thickness 20 ⁇ m).
• OPP Biaxially oriented polypropylene
• Example 1 Surface printing was performed using the printing method, white ink and color ink set shown in Table 3, and substrate 1 (PET film) as the substrate.
• Example 1 by drying the white ink (A) between cylinders, it did not peel off even with high-viscosity offset ink for post-printing, and showed good printability. Furthermore, the density of the color ink was stable even during continuous printing.
• Example 2 in which the amount of solvent in the ink (A) is small and in Example 3 in which the boiling point of the solvent in the ink (A) is high, the increase in the viscosity of the white ink after drying is small, and the printability is low.
• Example 3 in which the boiling point of the solvent in the ink (A) is high, the increase in the viscosity of the white ink after drying is small, and the printability is low.
• Example 4 in which water was used instead of the solvent in ink (A), also showed good printability and continuous printing stability.
• Example 5 in which a monomer containing an alicyclic skeleton was used, in addition to good printability and continuous printing stability, adhesion of the printed matter and abrasion resistance were also improved.
• Comparative Example 1 in which the ink (A) was also used as the color ink, by performing inter-drying for each color, good printability was shown for all colors, but the density fluctuation during continuous printing was large, and the printing was stable. sex was inadequate.
• Table 3 shows the printing conditions and evaluation results.
• Comparative Example 2 only flexo type ink (B) including white ink was used. In Comparative Example 2, white ink and preprinted color ink were picked up by the rear cylinder, color mixture occurred, color ink did not spread, and normal printing was not possible.
• Comparative Examples 3 and 4 only offset type ink (B) including white ink was used.
• the white ink was picked up by the rear cylinder and color mixture occurred.
• the color ink did not spread, and normal printing was not possible.
• the wet-on-wet printability and density stability were A, but the white ink leveling property was poor and the hiding property was insufficient.
• Table 3 shows the printing conditions and evaluation results.
• Example 7 Surface printing was carried out in the same manner as in Example 5, except that the base material was changed to base material 2 (PE film). Even if the base material was changed, the printability, hiding power and density stability were good. In addition, there was no peeling or peeling due to rubbing, which was good. Table 4 shows the results.
• Example 8 Surface printing was performed using printing method 5, EB varnish, white ink 1, color ink set 1 as overprint varnish, and substrate 3 (OPP film) as the substrate. As in Example 1 using printing method 1, the printability and hiding power were good, and the density of the color ink was stable. In addition, the coating of the overprint varnish was satisfactory without peeling or peeling due to rubbing. Table 4 shows the results.

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• 2022
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