WO2019069736A1 - Electron beam-curable water-based flexo ink for surface printing and boilable retort pouch using same - Google Patents

Electron beam-curable water-based flexo ink for surface printing and boilable retort pouch using same Download PDF

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Publication number
WO2019069736A1
WO2019069736A1 PCT/JP2018/035303 JP2018035303W WO2019069736A1 WO 2019069736 A1 WO2019069736 A1 WO 2019069736A1 JP 2018035303 W JP2018035303 W JP 2018035303W WO 2019069736 A1 WO2019069736 A1 WO 2019069736A1
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WIPO (PCT)
Prior art keywords
electron beam
water
ink
printing
surface printing
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Application number
PCT/JP2018/035303
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French (fr)
Japanese (ja)
Inventor
勉 春山
栄樹 伊藤
伸生 猿渡
歳徳 石橋
Original Assignee
Ｄｉｃグラフィックス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by Ｄｉｃグラフィックス株式会社 filed Critical Ｄｉｃグラフィックス株式会社
Priority to JP2019524478A priority Critical patent/JP6557799B1/en
Priority to CN201880061759.7A priority patent/CN111108159B/en
Priority to AU2018344119A priority patent/AU2018344119B9/en
Publication of WO2019069736A1 publication Critical patent/WO2019069736A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D33/00—Details of, or accessories for, sacks or bags
    • 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
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds

Definitions

  • the present invention relates to a water-based flexographic ink for surface printing that can be used for water-based flexographic printing equipped with an electron beam-curable device, and a pouch for boiling and retorting using the same.
  • Aqueous flexographic printing is widely used for the purpose of imparting cosmetic properties and functionality to a substrate.
  • Food pouches such as gas replacement pouches for snack packaging, pouches for boiling, pouches for heating, retort pouches for heating and pressing, due to recent changes in lifestyles such as the increase in the number of double-income households and the number of single-person households
  • consumption of pouches for boiled and retorted foods is increasing year by year.
  • Examples of boiled / retort pouches include packaging materials for food and drink such as curry, hamburger, pasta sauce, soup, bowls, etc.
  • the boiled pouch is, for example, 30 minutes to 60 minutes at a temperature of about 90 ° C. to 98 ° C.
  • the heat treatment is performed for about a minute, and the retort pouch is subjected to a heat and pressure treatment for about 20 to about 60 minutes, for example, at a temperature of about 110 ° C. to about 130 ° C. under pressurized conditions. Therefore, the ink used in the boil / retort pouch is also required to be able to withstand the above-mentioned heat and pressure test and to have durability such as abrasion resistance so as not to lose a print during transportation and storage.
  • packaging materials using water-based inks and solventless adhesives have been proposed, but sufficient adhesion strength is obtained with water-based inks and solventless adhesives using hydrophilic materials. It has not been possible to replace the conventional solvent-based ink / solvent-based adhesive composition. Furthermore, regardless of the combination of water-based or solvent-based ink, solvent-based or non-solvent-based adhesive, it is necessary to carry out lamination after back printing from the viewpoint of ink durability such as abrasion resistance, etc. Since the aging process can not be completed, it is not possible to shift to the processing and filling process immediately after printing. Therefore, there is a limit to shortening the delivery time in the conventional voile / retort packaging material using reverse printing.
  • the problem to be solved by the present invention is that the amount of VOC (Volatile Organic Compounds) in the ink is 0% as much as possible, and the electron beam curing is excellent in the abrasion resistance and the boiling / retortability on the outer surface of the pouch container. It is an object of the present invention to provide a surface-printed pouch for a boil / retort using an aqueous flexographic ink for surface printing.
  • VOC Volatile Organic Compounds
  • the present invention can solve the above-mentioned problems even in aqueous flexo printing by using an electron beam (EB) curable aqueous ink excellent in water resistance, heat resistance, abrasion resistance, etc. for surface printing of a boil / retort pouch.
  • EB electron beam
  • Electron beam (EB) curable aqueous ink forms a strong film by EB irradiation, so that it is possible to carry out the filling and processing steps immediately after the printing step, and it is possible to shorten the delivery time of the boil and retort packaging material I assume.
  • the present invention is an aqueous flexo ink for electron beam-curable surface printing comprising an aqueous resin (X), an electron beam polymerizable compound (Y) having an ethylenic double bond, a pigment and water.
  • the present invention relates to a water-based flexographic ink for electron beam curing surface printing.
  • the present invention is also directed to an electron beam-curable surface printing method, wherein the electron beam polymerizable compound (Y) having an ethylenic double bond is a water soluble (meth) acrylic monomer and / or a water soluble (meth) acrylic oligomer.
  • the electron beam polymerizable compound (Y) having an ethylenic double bond is a water soluble (meth) acrylic monomer and / or a water soluble (meth) acrylic oligomer.
  • the present invention also relates to an aqueous flexographic ink for electron beam curing surface printing, wherein the electron beam polymerizable compound (Y) having an ethylenic double bond is polyethylene glycol di (meth) acrylate.
  • the present invention also relates to a water-based flexographic ink for electron beam-curable surface printing, wherein the water-based resin (X) is a non-reactive water-based urethane resin.
  • the energy intensity of the electron beam is 30,000 to 300,000 eV, and the irradiation dose is 5 to 100 kGy ⁇ m / min.
  • the present invention relates to a water-based flexographic ink for electron beam curable surface printing, which is (kilo gray).
  • the present invention also relates to a printed matter obtained by printing on a plastic film using the aqueous flexographic ink for electron beam curing surface printing and the flexographic printing machine.
  • the present invention relates to a laminate obtained by laminating the obtained printed matter and a substrate through a laminating adhesive, and in particular, a pouch for boiling, a retort pouch, etc. for which heat resistance and water resistance are required. Can be suitably used.
  • the water-based flexographic ink for electron beam-curable surface printing of the present invention has a VOC content of 0% in the ink, and when used for printing the outer surface of a retort pouch container, its boil resistance such as abrasion resistance, water resistance and heat resistance -A pouch for boil retort excellent in retort suitability can be obtained.
  • the electron beam-curable surface printing aqueous flexo ink of the present invention comprises an aqueous resin (X), an electron beam polymerizable compound (Y) having an ethylenic double bond, a pigment, and water.
  • the most well-known layer structure is, for example, a composite film in which an aluminum foil is bonded to a polypropylene film as a base material using an adhesive and the aluminum foil is further bonded to a polyethylene terephthalate (sometimes referred to as PET hereinafter) film. is there.
  • PET film / ink layer for solvent type reverse printing / adhesive layer (needs aging) / aluminum foil or aluminum deposited film layer / adhesive layer / polypropylene base film
  • PET film / ink layer for solvent type reverse printing is referred to as the upper layer
  • aluminum foil or aluminum deposited film layer / adhesive layer / polypropylene substrate film is referred to as the lower layer.
  • the lower layer that is, "aluminum foil or aluminum-deposited film layer / adhesive layer / polypropylene base film” is integrated, and may be used.
  • the lower layer polypropylene base film is not limited to this, and other olefin films may be used.
  • the general processing procedure is as follows: after back printing with a solvent type reverse printing ink, an adhesive is applied and laminated with other required films, and if necessary, subjected to aging to produce a composite film, A retort pouch package made of the composite film is obtained. The contents are subjected to a filling process to form a retort pouch package.
  • the water-based flexographic ink for electron beam curing surface printing of the present invention is, from the top layer, electron beam curing water ink layer / PET film layer / adhesive layer / aluminum foil or aluminum deposited film layer / adhesive layer / polypropylene group It is a water-based flexographic ink for surface printing which can be used in a layer construction composed of a material film in order. This is because the electron beam curable aqueous ink is printed on the PET surface of the laminated film on which "PET film layer / adhesive layer / aluminum foil or aluminum deposited film layer / adhesive layer / polypropylene base film" is already laminated. It is possible.
  • the printing and laminating steps involve the emission of VOCs in the drying step.
  • the binder of the ink used is a water-based resin, and sufficient adhesive strength can not be obtained.
  • the types of ink and adhesive in the case of the packaging material by back printing / lamination processing, since an aging step is essential, delivery time is required and productivity is poor.
  • an electron beam (EB) -curable surface printing aqueous ink excellent in water resistance, heat resistance, and abrasion resistance is used on the surface of the laminated film prepared in advance and on which all layers other than the printing layer are laminated. Since the printing can be performed, the process from printing to bag-making and filling can be significantly shortened as compared with the manufacturing process of the packaging material having the laminating process after the conventional reverse printing and printing. In addition to shortening of delivery time and inventory reduction by shortening of such process time, significant cost reduction by layer reduction and volume reduction can be expected. Furthermore, since flexographic printing can perform high-speed printing, higher productivity can be realized.
  • an electron beam (EB) curable overprint varnish layer is further coated by a roll coater or the like on the front printing layer provided with the aqueous flexo ink for electron beam curing front printing of the present invention, and an electron beam (EB) ) Hardening can further improve abrasion resistance, surface gloss and the like.
  • the aqueous flexographic ink for electron beam-curable surface printing of the present invention is intended for surface printing on the outer surface of a retort pouch container, and has the abrasion resistance, water resistance, heat resistance, etc. required as boiling and retort suitability.
  • the aqueous resin (X) is essential from the viewpoint of providing both.
  • Water-soluble or dispersion-type (emulsion and dispersion) resins of various binder resins such as aqueous styrene-acrylic-maleic acid resins, aqueous polyurethane resins and aqueous polyester resins can be exemplified as preferable examples.
  • water-based aliphatic polyurethane dispersions or those obtained by dispersing urethane resin beads or beads in a water-based solvent also referred to as dispersion, and also including urethane resin dispersions, aliphatic polyurethane dispersions, etc.
  • a water-based solvent also referred to as dispersion, and also including urethane resin dispersions, aliphatic polyurethane dispersions, etc.
  • an aqueous polyurethane resin is preferable from the viewpoint of adhesion to a substrate, long run printability and the like.
  • a non-reactive water-based urethane resin is preferable.
  • aqueous resin (X) water-based urethane resin which has a (meth) acryloyl group.
  • aqueous resin (X) A commercially available product may be used as the aqueous resin (X). In that case, it is available as a dispersion or emulsion of aqueous resin.
  • an electron beam polymerizable compound (Y) having an ethylenic double bond is essential.
  • electron beam polymerizable compounds having an ethylenic double bond known electron beam curable monomers and oligomers can be used, but from the viewpoint of solubility in water, water soluble (meth) acrylic monomers, water soluble (Meth) acrylic oligomers are preferred.
  • water-soluble (meth) acrylate examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, N- (2-hydroxyethyl) acrylamide (abbreviation: HEAA), N- (2-hydroxyethyl) methacrylamide, N- (2-hydroxymethyl) acrylamide, N- (2-hydroxymethyl) methacrylamide, acryloyl morpholine, methylol acrylamide , Dimethyl acrylamide, methoxy methyl acrylamide, diethyl acrylamide, isopropyl acrylamide, polyethylene glycol di (meth) acrylate, etc. But it is, not to be limited to these.
  • water-soluble (meth) acrylic oligomers CN549, CN131, CN131B, CN2285, CN3100, CN3105, CN132, CN132, CN132, CN132 (Sartomer), Ebecryl 140, Ebecryl 1140, Ebecryl 40, Ebecryl 3200, Ebecryl 3201, Ebecryl 3212 ( Cytec Industries), PHOTOMER 3660, PHOTOMER 5006F, PHOTOMER 5429, PHOTOMER 5429F (Cognis), LAROMER PO 33F, LAROMER PO 43F, LAROMER PO 94F, LAROMER UO 35D, LAROMER PA 9039V, LAROMER PO 9026V, LAROME 8996, LAROMER 8765, LAROMER 8986 (BASF), and the like.
  • the water soluble (meth) acrylic monomer and the water soluble (meth) acrylic oligomer may be used alone or in combination. Among them, polyethylene
  • the aqueous resin is effective for imparting flexibility to the ink film after electron beam irradiation and improving adhesion to the substrate, but when the ratio of the aqueous resin portion increases, the double bond concentration in the ink coating film And there is a tendency to increase concerns such as poor curing, poor friction resistance, poor heat resistance, poor water resistance and the like.
  • the aqueous resin (X) is a commercial product, it is mostly in the form of a dispersion or emulsion of the aqueous resin, but in this case the dispersion of the aqueous resin or the dry solid content of the emulsion is employed. Do.
  • Examples of the pigment used in the water-based flexographic ink for electron beam-curable surface printing of the present invention include organic and inorganic pigments and dyes used in general inks, paints, recording agents and the like.
  • organic pigment examples include azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene pigments, perinone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, azomethine azo pigments, dictopyrrolopyrrole pigments, isoindoline pigments, etc. Pigments are listed.
  • the inorganic pigment examples include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, bengara, aluminum, mica (mica) and the like. Further, it is possible to use a bright pigment (Metashine; Nippon Sheet Glass Co., Ltd.) in which a metal flake or a metal oxide is coated on a glass flake or a massive flake as a base material. It is preferable to use titanium oxide for white ink, carbon black for black ink, aluminum for gold and silver ink, and mica for pearl ink from the viewpoint of cost and coloring power.
  • Aluminum is in the form of powder or paste, but is preferably used in the form of paste in terms of handleability and safety, and whether leafing or non-leafing is used is appropriately selected in terms of brightness and density.
  • the total amount of the pigments is preferably contained in an amount sufficient to secure the density and coloring strength of the ink, that is, in a proportion of 1 to 50% by mass with respect to the total weight of the ink.
  • a coloring agent can be used individually or in combination of 2 or more types.
  • the water-based flexographic ink for electron beam curing front printing of the present invention may further contain a solvent and other auxiliary agents according to the purpose.
  • a solvent water alone or an organic solvent miscible with water can be used.
  • the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and n-propyl alcohol, and polyhydric alcohols such as propylene glycol and glycerin, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n -Ethers such as propyl ether and ethyl carbitol.
  • various waxes such as paraffin wax, polyethylene wax, PTFE wax, carnauba wax, oleic acid amide, stearic acid amide, etc. for imparting abrasion resistance, slip resistance, etc.
  • Fatty acid amides such as erucic acid amide and various dispersants for improving the wetting of silicone based, non-silicon based antifoaming agents and pigments for suppressing foaming during printing, wetting agents for improving the wettability to a substrate, etc. Can be used as appropriate.
  • the aqueous flexo ink for electron beam-curable surface printing according to the present invention is produced using an Eiger mill, a sand mill, a gamma mill, an attritor, etc. which are generally used for the production of gravure and flexographic printing inks.
  • the aqueous flexo ink for electron beam curing surface printing of the present invention has a viscosity of 5 to 35 seconds at 25 ° C. when using Zan cup # 5 manufactured by Rigosha Co., Ltd., more preferably 8 to 20 seconds It is.
  • the viscosity in millipascal seconds may be in the range of 100 to 1000 (mPa ⁇ s) at 25 ° C., and more preferably in the range of 180 to 600 (mPa ⁇ s).
  • the surface tension at 25 ° C. of the aqueous flexographic ink for electron beam-curable surface printing of the present invention is preferably 25 to 50 mN / m, and more preferably 33 to 43 mN / m.
  • the aqueous flexographic ink for electron beam curing surface printing of the present invention is excellent in adhesion to various film substrates, and can be used for printing on thermoplastic resin films and plastic products.
  • the base film polyamide resins such as nylon (Ny) 6, nylon 66, nylon 46, etc., polyester resins such as PET, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, etc.
  • Biodegradable resin represented by aliphatic polyester resin such as polyhydroxycarboxylic acid such as polylactic acid, polyhydroxycarboxylic acid such as polylactic acid, poly (ethylene succinate), poly (butylene succinate), polyolefin such as polypropylene (PP), polyethylene Films made of thermoplastic resins such as resins, polyimide resins, polyarylate resins or mixtures thereof, and laminates thereof can be mentioned, among which films made of polyester, polyamide, polyethylene, polypropylene Preferably it can be used. These base films may be unstretched films or stretched films, and the production method is not limited. Also, the thickness of the base film is not particularly limited, but usually, it may be in the range of 1 to 500 ⁇ m. Moreover, it is preferable that the corona discharge process is carried out to the printing surface of a base film. In addition, silica, alumina or the like may be vapor deposited.
  • the aqueous flexographic ink for electron beam curing surface printing of the present invention is a layer composed of at least the electron beam curing aqueous ink layer / film layer / adhesive layer / aluminum foil / adhesive layer / substrate film from the upper layer
  • the surface printing only aqueous flexographic ink which can be used in the construction, and the two layers of the upper layer, “electron beam curable aqueous ink layer / film layer” correspond to a surface printing printed matter by film printing. Further, by providing an "electron beam curable aqueous OP varnish layer" on the upper layer of the "electron beam curable aqueous ink layer", the abrasion resistance and the gloss of the printed matter surface can be improved.
  • As the lower layer aluminum / adhesive layer / substrate film a substrate film previously deposited with aluminum or a high functional film having a multilayer structure may be used.
  • the aqueous flexo ink for electron beam curing surface printing of the present invention is an electron beam in which electrons are artificially accelerated by an accelerator to cure the ink film on the surface of a printed matter printed on a plastic film using a flexo printing machine.
  • a wire also called Electron Bearm EB.
  • the printed ink layer is formed as it is as an ink film, and in the case of an EB curable composition which does not contain a photopolymerization initiator unlike UV curing, the properties of the designed composition are directly reflected in the properties of the ink film.
  • the ink film completely polymerized by EB curing is characterized by no odor or low odor since it contains almost no low molecular components such as a photopolymerization initiator. Further, in the case of the EB curing process, since the influence of the heat given to the irradiated object is small, distortion, wrinkles, deformation and the like due to the heat to the thin film hardly occur. Further, EB curing enables high-speed processing at a line speed of 10 to 400 meters per minute or more, and UV curing does not provide the same effect while suppressing heat generation.
  • the energy intensity of the electron beam to be used is 30,000 to 300,000 eV, and the irradiation dose is 5 to 100 kGy ⁇ m / min. It is preferable that it is (kilogray).
  • the varnish is drawn by a roll coater or the like after printing in order to provide an "electron beam curable aqueous OP varnish layer" on the upper layer of the "electron beam curable aqueous ink layer", the ink layer and the OP varnish layer are Electron beam curing can be performed simultaneously with the wire.
  • a flexo ink according to the composition of Table 1 is prepared as an aqueous flexo ink for electron beam curing surface printing comprising an aqueous resin (X), an electron beam polymerizable compound (Y) having an ethylenic double bond, a pigment, and water. did.
  • Ink 1 a pigment dispersion base manufactured by DIC (WFJ R507 primary color base, containing 40% by mass of phthalocyanine pigment based on the dispersion base), non-reactive urethane dispersion, and aliphatic epoxy acrylate, (BASF Lamarar LR8765)
  • DIC WFJ R507 primary color base, containing 40% by mass of phthalocyanine pigment based on the dispersion base
  • non-reactive urethane dispersion aliphatic epoxy acrylate
  • Aqueous resin Non-reactive urethane dispersion (39 mass% non-volatile matter)
  • Electron beam polymerizable compound (Y) having ethylenic double bond Urethane acrylate (Water-based UV-curable resin manufactured by Daicel 35% solid content)
  • Aliphatic epoxy acrylate BASF Lamarar LR 8765
  • Polyethylene glycol diacrylate pigment ⁇ base (consisting of 40 mass% of WFJ R507 primary color ⁇ base phthalocyanine pigment manufactured by DIC based on the dispersion base)
  • Black base includes 40% by mass of DIC WFJ R805 black base black base carbon black with respect to the dispersion base)
  • Print method A laminated film for boiling and retort wrapping material was prepared in the order of "corona-treated polyethylene terephthalate (PET) film / adhesive layer / aluminum foil / adhesive layer / polypropylene base film" from the upper layer previously laminated.
  • the inks 1 to 5 obtained by the above-mentioned production method were surface-printed and printed on a CI 6-color flexographic printing machine (SOLOFLEX, manufactured by Windmoeller & Hoelscher).
  • SOLOFLEX CI 6-color flexographic printing machine
  • WFJ M1000 varnish EB curable OP varnish
  • Electron beam irradiation Immediately after printing, using an EB apparatus, the energy intensity is 80,000 eV and the irradiation dose is 60 kGy ⁇ m / min. Electron beam irradiation was performed at (kilo gray). In addition, since the irradiation dose differs depending on the pigment used for the ink, in curing of the inks 1, 2, 4, and 5 using ⁇ -based (WF J R507 primary color ⁇ -based manufactured by DIC), the anilox line number (line / cm) And a cell volume (cm 3 ) of 4.5.
  • Table 2 shows the anilox line number (line / cm) and cell volume (cm 3 ) in the case of using a black base (WF-R 805 black base manufactured by DIC) and in the case of an OP varnish containing no pigment. Show.
  • the printed laminated film for boiling and retort packaging material is referred to as "printed laminated film”.
  • Inks used in Examples 1 to 5 and Comparative Example 1 in Table 3, presence or absence of EB curable OP varnish layer, water content in ink, amount of non-reactive (non-electron beam curable) resin, electron beam polymerizable compound The amount, the non-reactive resin ratio to the amount of electron beam polymerizable compound 100, the amount of VOC in the ink, and the evaluation result of the printed laminated film are described.
  • the numerical values in Table 3 indicate "parts" on a mass basis.
  • the water-based flexographic ink for electron beam curing front printing of the present invention does not need to consider the amount of VOC (%) in the ink and does not require an aging time after printing.
  • the ink is excellent in abrasion resistance and boil / retort suitability.

Abstract

The present invention addresses the problem of providing a boilable retort pouch that is surface printed using an electron beam-curable water-based flexo ink for surface printing on the outside of the pouch container, wherein the amount of VOC in the ink is almost 0% and the ink has an excellent abrasion resistance and an excellent boilability and retortability. The electron beam-curable water-based flexo ink for surface printing contains a water-based resin (X), an ethylenic double bond-bearing electron beam-curable compound (Y), a pigment, and water, and is characterized in that the mass ratio between the solids fraction of the water-based resin (X) and the solids fraction of the ethylenic double bond-bearing electron beam-curable compound (Y) is within the range of (X)/(Y) = 5/100 to 400/100.

Description

電子線硬化型表刷り用水性フレキソインキ、及びそれを用いたボイル・レトルト用パウチWater-based flexographic ink for electron beam curing surface printing, and pouch for retort using it
　本発明は、電子線硬化型の装備を備える水性フレキソ印刷に使用可能な表刷り専用の水性フレキソインキ、及びそれを用いたボイル・レトルト用パウチに関する。 The present invention relates to a water-based flexographic ink for surface printing that can be used for water-based flexographic printing equipped with an electron beam-curable device, and a pouch for boiling and retorting using the same.
　水性フレキソ印刷は、被印刷体に美粧性、機能性を付与させる目的で広く用いられている。
　近年、共働き世帯数および単身世帯数の増加など近年のライフスタイルの変化により、食品用パウチ、たとえばスナック包装用のガス置換パウチ，加熱処理に対応したボイル用パウチ、加熱加圧処理対応のレトルトパウチなどが挙げられるが、中でもボイル・レトルト食品用パウチの消費量は年々増加している。
　ボイル・レトルトパウチの例としては、カレー、ハンバーグ、パスタソース、スープ、どんぶりの具等の飲食品用の包材が挙げられ、ボイルパウチは、例えば９０℃～９８℃程度の温度で３０分～６０分程度の加熱処理がなされ、レトルトパウチは、例えば加圧条件下１１０℃～１３０℃程度の温度で、約２０～６０分間程度の加熱加圧処理がなされる。
　そのため、ボイル・レトルトパウチに使用するインキに対しては、上記の加熱加圧試験に耐えうること、輸送・保存中に印刷が欠損しないための耐摩性等の耐久性も求められる。現行のボイル・レトルトパウチには，溶剤型インキを用いた裏刷り印刷物を溶剤型接着剤で貼り合わせたラミネート包材を用いるのが一般的だが、食への安全性と環境への意識の高まりから、より安全で環境負荷の低い構成から成る包材への転換が期待されている。 Aqueous flexographic printing is widely used for the purpose of imparting cosmetic properties and functionality to a substrate.
Food pouches, such as gas replacement pouches for snack packaging, pouches for boiling, pouches for heating, retort pouches for heating and pressing, due to recent changes in lifestyles such as the increase in the number of double-income households and the number of single-person households In particular, consumption of pouches for boiled and retorted foods is increasing year by year.
Examples of boiled / retort pouches include packaging materials for food and drink such as curry, hamburger, pasta sauce, soup, bowls, etc. The boiled pouch is, for example, 30 minutes to 60 minutes at a temperature of about 90 ° C. to 98 ° C. The heat treatment is performed for about a minute, and the retort pouch is subjected to a heat and pressure treatment for about 20 to about 60 minutes, for example, at a temperature of about 110 ° C. to about 130 ° C. under pressurized conditions.
Therefore, the ink used in the boil / retort pouch is also required to be able to withstand the above-mentioned heat and pressure test and to have durability such as abrasion resistance so as not to lose a print during transportation and storage. Although it is common to use a laminate packaging material in which solvent-based ink-backed printed matter is laminated with a solvent-type adhesive for current boiled / retort pouches, raising food safety and environmental awareness From this, it is expected that the packaging material will be converted to a safer, less environmental impact component.
　このような要求に対応するため、水性インキと無溶剤型接着剤を用いた包材が提案されているが、親水性原料を用いた水性インキと無溶剤型接着剤では十分な接着強度が得られず、従来の溶剤型インキ／溶剤型接着剤の構成から置き換えられないのが現状であった。
さらに水性または溶剤型インキ、溶剤型または無溶剤型接着剤の組み合わせに関わらず、耐摩性等のインキの耐久性の観点から、裏刷り印刷後にラミネート加工を実施する必要があり、ラミネート加工後のエージング工程を欠くことができず、印刷後ただちに加工・充填工程に移ることはできない。そのため、従来の裏刷り印刷を用いたボイル・レトルト包材では短納期化に限界があった。 In order to meet such requirements, packaging materials using water-based inks and solventless adhesives have been proposed, but sufficient adhesion strength is obtained with water-based inks and solventless adhesives using hydrophilic materials. It has not been possible to replace the conventional solvent-based ink / solvent-based adhesive composition.
Furthermore, regardless of the combination of water-based or solvent-based ink, solvent-based or non-solvent-based adhesive, it is necessary to carry out lamination after back printing from the viewpoint of ink durability such as abrasion resistance, etc. Since the aging process can not be completed, it is not possible to shift to the processing and filling process immediately after printing. Therefore, there is a limit to shortening the delivery time in the conventional voile / retort packaging material using reverse printing.
　α，β－エチレン系不飽和輻射線重合性二重結合を含む水溶性化合物と水からなる高エネルギー線硬化性水性組成物を示す発明がなされているが、耐摩耗性、及びレトルトパウチで必須とされるボイル・レトルト性の点で十分であるとは言えない（例えば、特許文献１～３）。 It has been invented to show a high energy ray curable aqueous composition consisting of a water soluble compound containing an α, β-ethylenically unsaturated radiation polymerizable double bond and water, but the wear resistance, and the retort pouch are essential It can not be said that it is sufficient in the point of boiled retortability (for example, Patent Documents 1 to 3).
特開２００３－１４７００１号公報JP 2003-147001 A 特開２００３－１４７２３０号公報JP 2003-147230 A 特開２００８－１５０６１０号公報JP 2008-150610 A
　本発明が解決しようとする課題は、インキ中のＶＯＣ（揮発性有機化合物（Volatile Organic Compounds））量が限りなく０％であり、パウチ容器外面に耐摩性、ボイル・レトルト適性に優れる電子線硬化型表刷り用水性フレキソインキを用いて表刷り印刷されたボイル・レトルト用パウチを提供することである。 The problem to be solved by the present invention is that the amount of VOC (Volatile Organic Compounds) in the ink is 0% as much as possible, and the electron beam curing is excellent in the abrasion resistance and the boiling / retortability on the outer surface of the pouch container. It is an object of the present invention to provide a surface-printed pouch for a boil / retort using an aqueous flexographic ink for surface printing.
　本発明者等は、上記の課題を解決すべく鋭意研究した結果、電子線硬化型の装備を備える水性フレキソ印刷に使用可能な表刷り専用の水性フレキソインキの組成に特に好ましい樹脂、電子線重合性化合物に顔料、水を加える事により、前記課題を解決できることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have found that resins, electron beam polymerization, are particularly preferable for the composition of aqueous flexographic inks for surface printing that can be used for aqueous flexographic printing equipped with an electron beam curing type equipment. It has been found that the problem can be solved by adding a pigment and water to the organic compound, and the present invention has been completed.
　本発明は耐水性、耐熱性、耐摩性等に優れた電子線（ＥＢ）硬化型水性インキをボイル・レトルトパウチの表刷りに用いることで水性フレキソ印刷であっても上記の課題を解決できることを見出したものである。すなわち事前にラミネート済みの原紙を準備しておき、受注とともに直ちに原紙表面に印刷を施す。電子線（ＥＢ）硬化型水性インキはＥＢ照射により強固な被膜を形成するため、印刷工程終了後、直ちに充填・加工工程を実施することが可能となり、ボイル・レトルト包材の短納期化を可能とする。 The present invention can solve the above-mentioned problems even in aqueous flexo printing by using an electron beam (EB) curable aqueous ink excellent in water resistance, heat resistance, abrasion resistance, etc. for surface printing of a boil / retort pouch. I found it. That is, a laminated base paper is prepared in advance, and printing is performed on the surface of the base paper immediately upon receipt of an order. Electron beam (EB) curable aqueous ink forms a strong film by EB irradiation, so that it is possible to carry out the filling and processing steps immediately after the printing step, and it is possible to shorten the delivery time of the boil and retort packaging material I assume.
　すなわち、本発明は、　水性樹脂（Ｘ）、エチレン性二重結合を有する電子線重合性化合物（Ｙ）、顔料、及び水を含有する電子線硬化型表刷り用水性フレキソインキであって、前記水性樹脂（Ｘ）の固形分とエチレン性二重結合を有する電子線重合性化合物（Ｙ）固形分の質量比が、（Ｘ）／（Ｙ）＝５／１００～４００／１００の範囲である電子線硬化型表刷り用水性フレキソインキに関する。 That is, the present invention is an aqueous flexo ink for electron beam-curable surface printing comprising an aqueous resin (X), an electron beam polymerizable compound (Y) having an ethylenic double bond, a pigment and water. The mass ratio of the solid content of the aqueous resin (X) and the solid content of the electron beam polymerizable compound (Y) having an ethylenic double bond is in the range of (X) / (Y) = 5/100 to 400/100. The present invention relates to a water-based flexographic ink for electron beam curing surface printing.
　また、本発明は、前記エチレン性二重結合を有する電子線重合性化合物（Ｙ）が、水溶性(メタ)アクリルモノマー及び／又は水溶性（メタ）アクリルオリゴマーである電子線硬化型表刷り用水性フレキソインキに関する。 The present invention is also directed to an electron beam-curable surface printing method, wherein the electron beam polymerizable compound (Y) having an ethylenic double bond is a water soluble (meth) acrylic monomer and / or a water soluble (meth) acrylic oligomer. Water-based flexographic ink
　また、本発明は、前記エチレン性二重結合を有する電子線重合性化合物（Ｙ）が、ポリエチレングリコールジ（メタ）アクリレートである電子線硬化型表刷り用水性フレキソインキに関する。 The present invention also relates to an aqueous flexographic ink for electron beam curing surface printing, wherein the electron beam polymerizable compound (Y) having an ethylenic double bond is polyethylene glycol di (meth) acrylate.
　また、本発明は、前記水性樹脂（Ｘ）が、非反応性水性ウレタン樹脂である電子線硬化型表刷り用水性フレキソインキに関する。 The present invention also relates to a water-based flexographic ink for electron beam-curable surface printing, wherein the water-based resin (X) is a non-reactive water-based urethane resin.
　また、本発明は、前記電子線のエネルギー強度が３０,０００～３００,０００ｅＶであり、照射線量が５～１００ｋＧｙ・ｍ／ｍｉｎ．（キログレイ）である電子線硬化型表刷り用水性フレキソインキに関する。 In the present invention, the energy intensity of the electron beam is 30,000 to 300,000 eV, and the irradiation dose is 5 to 100 kGy · m / min. The present invention relates to a water-based flexographic ink for electron beam curable surface printing, which is (kilo gray).
　また、本発明は、プラスチックフィルムに該電子線硬化型表刷り用水性フレキソインキ、及びフレキソ印刷機を用いて印刷してなる印刷物に関する。 The present invention also relates to a printed matter obtained by printing on a plastic film using the aqueous flexographic ink for electron beam curing surface printing and the flexographic printing machine.
　更に、本発明は、得られた印刷物と基材とを、ラミネート接着剤を介して、ラミネートしてなる積層体に関するもので、特に耐熱性や耐水性が要求されるボイル用パウチやレトルトパウチ等に好適に用いることができる。 Furthermore, the present invention relates to a laminate obtained by laminating the obtained printed matter and a substrate through a laminating adhesive, and in particular, a pouch for boiling, a retort pouch, etc. for which heat resistance and water resistance are required. Can be suitably used.
　本発明の電子線硬化型表刷り用水性フレキソインキは、インキ中のＶＯＣ量が０％であり、レトルトパウチ容器外面の印刷に用いた場合、その耐摩耗性、耐水性や耐熱性等のボイル・レトルト適性に優れたボイル・レトルト用パウチ得ることができる。 The water-based flexographic ink for electron beam-curable surface printing of the present invention has a VOC content of 0% in the ink, and when used for printing the outer surface of a retort pouch container, its boil resistance such as abrasion resistance, water resistance and heat resistance -A pouch for boil retort excellent in retort suitability can be obtained.
　本発明の電子線硬化型表刷り用水性フレキソインキは、水性樹脂（Ｘ）、エチレン性二重結合を有する電子線重合性化合物（Ｙ）、顔料、及び水を含有する電子線硬化型表刷り用水性フレキソインキであって、前記水性樹脂（Ｘ）の固形分とエチレン性二重結合を有する電子線重合性化合物（Ｙ）固形分の質量比が、（Ｘ）／（Ｙ）＝５／１００～４００／１００の範囲であることを特徴とする電子線硬化型表刷り用水性フレキソインキである。 The electron beam-curable surface printing aqueous flexo ink of the present invention comprises an aqueous resin (X), an electron beam polymerizable compound (Y) having an ethylenic double bond, a pigment, and water. A water-based flexo ink, wherein the mass ratio of the solid content of the aqueous resin (X) and the solid content of the electron beam-polymerizable compound (Y) having an ethylenic double bond is (X) / (Y) = 5/1. It is a water-based flexographic ink for electron beam curing front printing characterized in that it is in the range of 100 to 400/100.
　ここで、レトルトパウチ包装の最も単純な層構成について説明する。
従来最もよく知られた層構成は、例えば基材のポリプロピレンフィルムに接着剤を用いてアルミ箔を貼り合わせ、さらにアルミ箔をポリエチレンテレフタレート（以後ＰＥＴと称する場合がある）フィルムと貼り合わせる複合フィルムである。
該複合フィルムに印刷層を設けてある場合は、上層からＰＥＴフィルム／溶剤型裏刷り用インキ層／接着剤層（エージング要）／アルミ箔やアルミ蒸着フィルム層／接着剤層／ポリプロピレン基材フィルムの順であることが多く（以後「ＰＥＴフィルム／溶剤型裏刷り用インキ層」までを上層と称し、「アルミ箔やアルミ蒸着フィルム層／接着剤層／ポリプロピレン基材フィルム」までを下層と称する場合がある。）、その製造方法は、ＰＥＴフィルムへ溶剤型裏刷り用インキを用いて裏刷り印刷し、その後接着剤を塗布し、アルミ箔やアルミ蒸着フィルムと貼り合わせるのが一般的である。なお下層即ち「アルミ箔やアルミ蒸着フィルム層／接着剤層／ポリプロピレン基材フィルム」が一体型となっている高機能フィルムがありそれを利用する場合もある。下層のポリプロピレン基材フィルムはこれに限定されず他のオレフィン系フィルムを使用する場合もある。
一般的な加工手順は、溶剤型裏刷り用インキによる裏刷り印刷後、接着剤を塗布して必要な他のフィルムとラミネートし、必要に応じたエージングを施して複合フィルムを製造したのち、該複合フィルムを製袋したレトルトパウチ包装体を得る。これに内容物を充填工程しレトルトパウチ包装となる。 Here, the simplest layer structure of retort pouch packaging is demonstrated.
The most well-known layer structure is, for example, a composite film in which an aluminum foil is bonded to a polypropylene film as a base material using an adhesive and the aluminum foil is further bonded to a polyethylene terephthalate (sometimes referred to as PET hereinafter) film. is there.
When the printing layer is provided on the composite film, from the upper layer: PET film / ink layer for solvent type reverse printing / adhesive layer (needs aging) / aluminum foil or aluminum deposited film layer / adhesive layer / polypropylene base film In most cases (hereinafter referred to as "PET film / ink layer for solvent type reverse printing" is referred to as the upper layer, and "aluminum foil or aluminum deposited film layer / adhesive layer / polypropylene substrate film" is referred to as the lower layer). In some cases, it is common practice to back print on a PET film using solvent-based back printing ink, then apply an adhesive and bond it to an aluminum foil or aluminum vapor deposited film . There are high-performance films in which the lower layer, that is, "aluminum foil or aluminum-deposited film layer / adhesive layer / polypropylene base film" is integrated, and may be used. The lower layer polypropylene base film is not limited to this, and other olefin films may be used.
The general processing procedure is as follows: after back printing with a solvent type reverse printing ink, an adhesive is applied and laminated with other required films, and if necessary, subjected to aging to produce a composite film, A retort pouch package made of the composite film is obtained. The contents are subjected to a filling process to form a retort pouch package.
　一方で、本発明の電子線硬化型表刷り用水性フレキソインキは、上層から電子線硬化型水性インキ層／ＰＥＴフィルム層／接着剤層／アルミ箔やアルミ蒸着フィルム層／接着剤層／ポリプロピレン基材フィルムの順で構成される層構成で使用できる表刷り専用水性フレキソインキである。これは、予め「ＰＥＴフィルム層／接着剤層／アルミ箔やアルミ蒸着フィルム層／接着剤層／ポリプロピレン基材フィルム」までが既に積層された積層フィルムのＰＥＴ面に電子線硬化型水性インキを印刷することが可能である。 On the other hand, the water-based flexographic ink for electron beam curing surface printing of the present invention is, from the top layer, electron beam curing water ink layer / PET film layer / adhesive layer / aluminum foil or aluminum deposited film layer / adhesive layer / polypropylene group It is a water-based flexographic ink for surface printing which can be used in a layer construction composed of a material film in order. This is because the electron beam curable aqueous ink is printed on the PET surface of the laminated film on which "PET film layer / adhesive layer / aluminum foil or aluminum deposited film layer / adhesive layer / polypropylene base film" is already laminated. It is possible.
　従来の溶剤型裏刷り用インキと接着剤を用いた場合、印刷およびラミネート工程で、乾燥工程でのＶＯＣの排出を伴う。また、水性フレキソインキと無溶剤型接着剤の組み合わせでは、ＶＯＣ排出量を低減できるものの、使用するインキのバインダーが水性樹脂のため十分な接着強度が得られない。またインキと接着剤の種類に関わらず、裏刷り／ラミネート加工による包材では、エージング工程が必須となるため納期がかかり生産性に劣る。
一方本願では、予め準備された、印刷層以外の全ての層が積層された積層フィルムの表面に、耐水性、耐熱性、耐摩性に優れる電子線（ＥＢ）硬化型表刷り用水性インキを使用し印刷できるので、従来の裏刷り印刷後ラミネート工程を有する包材の製造工程と比較し、印刷から製袋・充填までの工程を大幅に短縮することが出来る。
　このような工程時間の短縮による短納期化や在庫削減に加え、減層・減容化による大幅なコストダウンも期待できる。さらにフレキソ印刷は高速印刷が可能であるため、より高い生産性を実現することができる。
　また、本発明の電子線硬化型表刷り用水性フレキソインキを設けた表刷り印刷層の上に、更に電子線（ＥＢ）硬化型オーバープリントニス層をロールコーター等で塗布し、電子線（ＥＢ）硬化させれば、耐摩耗性・表面の光沢等がさらに向上させる事が出来る。 In the case of using conventional solvent-based back printing inks and adhesives, the printing and laminating steps involve the emission of VOCs in the drying step. In addition, although the combination of the water-based flexographic ink and the solventless adhesive can reduce the amount of VOC emissions, the binder of the ink used is a water-based resin, and sufficient adhesive strength can not be obtained. In addition, regardless of the types of ink and adhesive, in the case of the packaging material by back printing / lamination processing, since an aging step is essential, delivery time is required and productivity is poor.
On the other hand, in the present application, an electron beam (EB) -curable surface printing aqueous ink excellent in water resistance, heat resistance, and abrasion resistance is used on the surface of the laminated film prepared in advance and on which all layers other than the printing layer are laminated. Since the printing can be performed, the process from printing to bag-making and filling can be significantly shortened as compared with the manufacturing process of the packaging material having the laminating process after the conventional reverse printing and printing.
In addition to shortening of delivery time and inventory reduction by shortening of such process time, significant cost reduction by layer reduction and volume reduction can be expected. Furthermore, since flexographic printing can perform high-speed printing, higher productivity can be realized.
In addition, an electron beam (EB) curable overprint varnish layer is further coated by a roll coater or the like on the front printing layer provided with the aqueous flexo ink for electron beam curing front printing of the present invention, and an electron beam (EB) ) Hardening can further improve abrasion resistance, surface gloss and the like.
　本発明の電子線硬化型表刷り用水性フレキソインキは、レトルトパウチ容器外面の表刷り用途を対象としたものであり、ボイル・レトルト適性として要求される耐摩耗性、耐水性や耐熱性等を兼備する観点から水性樹脂（Ｘ）が必須である。
　前記水性樹脂（Ｘ）としては、アクリル酸あるいはメタクリル酸とそのアルキルエステル、あるいはスチレン等を主なモノマー成分として共重合した水性アクリル系樹脂、水性スチレン－アクリル系樹脂、水性スチレン－マレイン酸系樹脂、水性スチレン－アクリル－マレイン酸系樹脂、水性ポリウレタン系樹脂、水性ポリエステル系樹脂などの各種バインダー樹脂の水溶型または分散型（エマルジョンおよびディスパージョン）樹脂が好適な例として例示できる。ウレタン樹脂ビーズ又はビーズを水系の溶剤に分散したものや（分散物とも呼ぶ。又、ウレタン樹脂分散物、脂肪族ポリウレタン分散物等、含む）、水系脂肪族ポリウレタンディスパージョンを用いることができる。基材への密着性，ロングラン印刷適性等の観点から，前記樹脂の中でも水性ポリウレタン樹脂が好ましい。
　また、更にインキ化した際のインキの臭気、包材としてのマイグレーションの観点から、非反応性水性ウレタン樹脂である事が好ましい。また、(メタ)アクリロイル基を有する反応性水性ウレタン樹脂と混合して用いてもよい。
水性樹脂（Ｘ）は市販品を用いてもよい。その場合、水性樹脂のディスパージョンやエマルジョンとして入手が可能である。 The aqueous flexographic ink for electron beam-curable surface printing of the present invention is intended for surface printing on the outer surface of a retort pouch container, and has the abrasion resistance, water resistance, heat resistance, etc. required as boiling and retort suitability. The aqueous resin (X) is essential from the viewpoint of providing both.
An aqueous acrylic resin, an aqueous styrene-acrylic resin, an aqueous styrene-maleic acid resin obtained by copolymerizing acrylic acid or methacrylic acid and its alkyl ester, or styrene as a main monomer component as the aqueous resin (X) Water-soluble or dispersion-type (emulsion and dispersion) resins of various binder resins such as aqueous styrene-acrylic-maleic acid resins, aqueous polyurethane resins and aqueous polyester resins can be exemplified as preferable examples. It is possible to use water-based aliphatic polyurethane dispersions or those obtained by dispersing urethane resin beads or beads in a water-based solvent (also referred to as dispersion, and also including urethane resin dispersions, aliphatic polyurethane dispersions, etc.). Among the above-mentioned resins, an aqueous polyurethane resin is preferable from the viewpoint of adhesion to a substrate, long run printability and the like.
Further, from the viewpoint of the odor of the ink when the ink is further formed and the migration as a packaging material, a non-reactive water-based urethane resin is preferable. Moreover, you may mix and use with the reactive aqueous | water-based urethane resin which has a (meth) acryloyl group.
A commercially available product may be used as the aqueous resin (X). In that case, it is available as a dispersion or emulsion of aqueous resin.
　本発明の電子線硬化型表刷り用水性フレキソインキでは、エチレン性二重結合を有する電子線重合性化合物（Ｙ）を必須とする。エチレン性二重結合を有する電子線重合性化合物としては、公知の電子線硬化型モノマーやオリゴマーを使用することができるが，水への溶解性の観点から水溶性(メタ)アクリルモノマー、水溶性（メタ）アクリルオリゴマーが好ましい。
　水溶性（メタ）アクリレートの具体例としては、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、Ｎ－（２－ヒドロキシエチル）アクリルアミド（略称：ＨＥＡＡ）、Ｎ－（２－ヒドロキシエチル）メタクリルアミド、Ｎ－（２－ヒドロキシメチル）アクリルアミド、Ｎ－（２－ヒドロキシメチル）メタクリルアミド、アクリロイルモルホリン、メチロールアクリルアミド、ジメチルアクリルアミド、メトキシメチルアクリルアミド、ジエチルアクリルアミド、イソプロピルアクリルアミド、ポリエチレングリコールジ（メタ）アクリレート等を挙げることができるが、これらに限定される訳ではない。 In the electron beam-curable surface printing aqueous flexo ink of the present invention, an electron beam polymerizable compound (Y) having an ethylenic double bond is essential. As electron beam polymerizable compounds having an ethylenic double bond, known electron beam curable monomers and oligomers can be used, but from the viewpoint of solubility in water, water soluble (meth) acrylic monomers, water soluble (Meth) acrylic oligomers are preferred.
Specific examples of the water-soluble (meth) acrylate include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, N- (2-hydroxyethyl) acrylamide (abbreviation: HEAA), N- (2-hydroxyethyl) methacrylamide, N- (2-hydroxymethyl) acrylamide, N- (2-hydroxymethyl) methacrylamide, acryloyl morpholine, methylol acrylamide , Dimethyl acrylamide, methoxy methyl acrylamide, diethyl acrylamide, isopropyl acrylamide, polyethylene glycol di (meth) acrylate, etc. But it is, not to be limited to these.
　水溶性（メタ）アクリルオリゴマーとしては、ＣＮ５４９、ＣＮ１３１、ＣＮ１３１Ｂ、ＣＮ２２８５、ＣＮ　３１００、ＣＮ３１０５、ＣＮ１３２、ＣＮ１３３、ＣＮ　１３２（Ｓａｒｔｏｍｅｒ）、Ｅｂｅｃｒｙｌ１４０、Ｅｂｅｃｒｙｌ　１１４０、Ｅｂｅｃｒｙｌ　４０、Ｅｂｅｃｒｙｌ　３２００、Ｅｂｅｃｒｙｌ　３２０１、Ｅｂｅｃｒｙｌ　３２１２（Ｃｙｔｅｃ　Ｉｎｄｕｓｔｒｉｅｓ）、ＰＨＯＴＯＭＥＲ　３６６０、ＰＨＯＴＯＭＥＲ　５００６Ｆ、ＰＨＯＴＯＭＥＲ　５４２９、ＰＨＯＴＯＭＥＲ　５４２９Ｆ（Ｃｏｇｎｉｓ）、ＬＡＲＯＭＥＲ　ＰＯ　３３Ｆ、ＬＡＲＯＭＥＲ　ＰＯ　４３Ｆ、ＬＡＲＯＭＥＲ　ＰＯ　９４Ｆ、ＬＡＲＯＭＥＲ　ＵＯ　３５Ｄ、ＬＡＲＯＭＥＲ　ＰＡ　９０３９Ｖ、ＬＡＲＯＭＥＲ　ＰＯ　９０２６Ｖ、ＬＡＲＯＭＥＲ　８９９６、ＬＡＲＯＭＥＲ　８７６５、ＬＡＲＯＭＥＲ　８９８６（ＢＡＳＦ）などが挙げられる。
水溶性(メタ)アクリルモノマー、水溶性（メタ）アクリルオリゴマーはそれぞれ単独で用いても、混合して用いてもよい。中でも、ポリエチレングリコールジ（メタ）アクリレートが好ましい。 As water-soluble (meth) acrylic oligomers, CN549, CN131, CN131B, CN2285, CN3100, CN3105, CN132, CN132, CN132, CN132 (Sartomer), Ebecryl 140, Ebecryl 1140, Ebecryl 40, Ebecryl 3200, Ebecryl 3201, Ebecryl 3212 ( Cytec Industries), PHOTOMER 3660, PHOTOMER 5006F, PHOTOMER 5429, PHOTOMER 5429F (Cognis), LAROMER PO 33F, LAROMER PO 43F, LAROMER PO 94F, LAROMER UO 35D, LAROMER PA 9039V, LAROMER PO 9026V, LAROME 8996, LAROMER 8765, LAROMER 8986 (BASF), and the like.
The water soluble (meth) acrylic monomer and the water soluble (meth) acrylic oligomer may be used alone or in combination. Among them, polyethylene glycol di (meth) acrylate is preferable.
　本発明の電子線硬化型表刷り用水性フレキソインキ中の前記水性樹脂（Ｘ）の固形分とエチレン性二重結合を有する電子線重合性化合物（Ｙ）固形分の質量比は、（Ｘ）／（Ｙ）＝５／１００～４００／１００の範囲であることを必須とする。
より望ましくは（Ｘ）／（Ｙ）＝７／１００～２５０／１００であり、更に望ましくは、（Ｘ）／（Ｙ）＝７／１００～５０／１００の範囲であり、最も望ましくは、（Ｘ）／（Ｙ）＝７／１００～２５／１００の範囲である。
この質量比率に関して、水性樹脂は電子線照射後のインキ皮膜の柔軟性付与や基材への密着性向上に有効であるが、水性樹脂部の比率が多くなるとインキ塗膜中の二重結合濃度が低下し、硬化不良、耐摩擦性不良、耐熱性不良、耐水性不良等の懸念が高まる傾向にある。
なお、前記水性樹脂（Ｘ）が市販品の場合は、水性樹脂のディスパージョンやエマルジョンとなっていることが殆どであるが、この場合は該水性樹脂のディスパージョンやエマルジョンの乾燥固形分を採用する。 The mass ratio of the solid content of the aqueous resin (X) and the electron beam polymerizable compound (Y) having an ethylenic double bond in the aqueous flexo ink for electron beam curing surface printing of the present invention is (X) It is essential that the range is / (Y) = 5/100 to 400/100.
More preferably, (X) / (Y) = 7/100 to 250/100, still more preferably, (X) / (Y) = 7/100 to 50/100, and most preferably X) / (Y) = 7/100 to 25/100.
With respect to this mass ratio, the aqueous resin is effective for imparting flexibility to the ink film after electron beam irradiation and improving adhesion to the substrate, but when the ratio of the aqueous resin portion increases, the double bond concentration in the ink coating film And there is a tendency to increase concerns such as poor curing, poor friction resistance, poor heat resistance, poor water resistance and the like.
In the case where the aqueous resin (X) is a commercial product, it is mostly in the form of a dispersion or emulsion of the aqueous resin, but in this case the dispersion of the aqueous resin or the dry solid content of the emulsion is employed. Do.
　本発明の電子線硬化型表刷り用水性フレキソインキで使用する顔料としては、例えば、一般のインキ、塗料、および記録剤などに使用されている有機、無機顔料や染料を挙げることができる。 Examples of the pigment used in the water-based flexographic ink for electron beam-curable surface printing of the present invention include organic and inorganic pigments and dyes used in general inks, paints, recording agents and the like.
　前記有機顔料としては、アゾ系、フタロシアニン系、アントラキノン系、ペリレン系、ペリノン系、キナクリドン系、チオインジゴ系、ジオキサジン系、イソインドリノン系、キノフタロン系、アゾメチンアゾ系、ジクトピロロピロール系、イソインドリン系などの顔料が挙げられる。 Examples of the organic pigment include azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene pigments, perinone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, azomethine azo pigments, dictopyrrolopyrrole pigments, isoindoline pigments, etc. Pigments are listed.
　前記無機顔料としては、カーボンブラック、酸化チタン、酸化亜鉛、硫化亜鉛、硫酸バリウム、炭酸カルシウム、酸化クロム、シリカ、ベンガラ、アルミニウム、マイカ（雲母）などが挙げられる。また、ガラスフレークまたは塊状フレークを母材とした上に金属、もしくは金属酸化物をコートした光輝性顔料（メタシャイン；日本板硝子株式会社）を使用できる。白インキには酸化チタン、墨インキにはカーボンブラック、金、銀インキにはアルミニウム、パールインキにはマイカ（雲母）を使用することがコストや着色力の点から好ましい。アルミニウムは粉末またはペースト状であるが、取扱い性および安全性の面からペースト状で使用するのが好ましく、リーフィングまたはノンリーフィングを使用するかは輝度感および濃度の点から適宜選択される。
　前記顔料の総計はインキの濃度・着色力を確保するのに充分な量、すなわちインキの総重量に対して１～５０質量％の割合で含まれることが好ましい。また、着色剤は単独で、または２種以上を併用して用いることができる。 Examples of the inorganic pigment include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, bengara, aluminum, mica (mica) and the like. Further, it is possible to use a bright pigment (Metashine; Nippon Sheet Glass Co., Ltd.) in which a metal flake or a metal oxide is coated on a glass flake or a massive flake as a base material. It is preferable to use titanium oxide for white ink, carbon black for black ink, aluminum for gold and silver ink, and mica for pearl ink from the viewpoint of cost and coloring power. Aluminum is in the form of powder or paste, but is preferably used in the form of paste in terms of handleability and safety, and whether leafing or non-leafing is used is appropriately selected in terms of brightness and density.
The total amount of the pigments is preferably contained in an amount sufficient to secure the density and coloring strength of the ink, that is, in a proportion of 1 to 50% by mass with respect to the total weight of the ink. Moreover, a coloring agent can be used individually or in combination of 2 or more types.
　本発明の電子線硬化型表刷り用水性フレキソインキは、更に、溶剤、その他目的に応じた助剤を使用することができる。
　前記溶剤としては、水単独または水と混和する有機溶剤を使用することができる。有機溶剤としては、例えばメチルアルコール、エチルアルコール、イソプロピルアルコール、ｎ－プロピルアルコール等のアルコール類やプロピレングリコール、グリセリン等の多価アルコール類、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノｎ－プロピルエーテル、エチルカルビトール等のエーテル類等がある。 The water-based flexographic ink for electron beam curing front printing of the present invention may further contain a solvent and other auxiliary agents according to the purpose.
As the solvent, water alone or an organic solvent miscible with water can be used. Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and n-propyl alcohol, and polyhydric alcohols such as propylene glycol and glycerin, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n -Ethers such as propyl ether and ethyl carbitol.
　また、その他の助剤成分としては、耐摩擦性、滑り性等を付与するためのパラフィン系ワックス、ポリエチレン系ワックス、ＰＴＦＥ系ワックス、カルナバワックス等の各種ワックス類やオレイン酸アミド、ステアリン酸アミド、エルカ酸アミド等の脂肪酸アミド類及び印刷時の発泡を抑制するためのシリコン系、非シリコン系消泡剤及び顔料の濡れを向上させる各種分散剤、基材への濡れ性を向上させる濡れ剤等を適宜使用することもできる。 Further, as other auxiliary agent components, various waxes such as paraffin wax, polyethylene wax, PTFE wax, carnauba wax, oleic acid amide, stearic acid amide, etc. for imparting abrasion resistance, slip resistance, etc. Fatty acid amides such as erucic acid amide and various dispersants for improving the wetting of silicone based, non-silicon based antifoaming agents and pigments for suppressing foaming during printing, wetting agents for improving the wettability to a substrate, etc. Can be used as appropriate.
　本発明に係わる電子線硬化型表刷り用水性フレキソインキは、グラビア、フレキソ印刷インキの製造に一般的に使用されているアイガーミル、サンドミル、ガンマミル、アトライター等を用いて製造される。
　本発明の電子線硬化型表刷り用水性フレキソインキは、その粘度が離合社製ザーンカップ＃５を使用した場合、２５℃にて５～３５秒であればよく、より好ましくは８～２０秒である。ミリパスカル秒で粘度を示すと、２５℃にて１００～１０００（ｍＰａ・ｓ）の範囲であればよく、より好ましくは１８０～６００（ｍＰａ・ｓ）の範囲である。
　また、本発明の電子線硬化型表刷り用水性フレキソインキの２５℃における表面張力は、２５～５０ｍＮ／ｍが好ましく、３３～４３ｍＮ／ｍであればより好ましい。該インキの表面張力が低いほどフィルム等の基材へのインキの濡れ性は向上するが、表面張力が２５ｍＮ／ｍを下回ると該インキの濡れ広がりにより、中間調の網点部分で隣り合う網点どうしが繋がり、ドットブリッジと呼ばれる印刷面の汚れの原因となる傾向にある。一方、該インキの表面張力が５０ｍＮ／ｍを上回ると、フィルム等の基材へのインキの濡れ性が低下しやすく、ハジキの原因となる傾向にある。 The aqueous flexo ink for electron beam-curable surface printing according to the present invention is produced using an Eiger mill, a sand mill, a gamma mill, an attritor, etc. which are generally used for the production of gravure and flexographic printing inks.
When the aqueous flexo ink for electron beam curing surface printing of the present invention has a viscosity of 5 to 35 seconds at 25 ° C. when using Zan cup # 5 manufactured by Rigosha Co., Ltd., more preferably 8 to 20 seconds It is. The viscosity in millipascal seconds may be in the range of 100 to 1000 (mPa · s) at 25 ° C., and more preferably in the range of 180 to 600 (mPa · s).
The surface tension at 25 ° C. of the aqueous flexographic ink for electron beam-curable surface printing of the present invention is preferably 25 to 50 mN / m, and more preferably 33 to 43 mN / m. The lower the surface tension of the ink, the better the wettability of the ink to the substrate such as a film, but if the surface tension is less than 25 mN / m, the ink spreads by the ink and the adjacent nets in the halftone dot portion The dots tend to be connected to cause contamination of the printing surface called a dot bridge. On the other hand, when the surface tension of the ink exceeds 50 mN / m, the wettability of the ink to a substrate such as a film tends to be reduced, which tends to cause repelling.
　本発明の電子線硬化型表刷り用水性フレキソインキは、各種のフィルム基材と密着性に優れ、熱可塑性樹脂フィルム、プラスチック製品への印刷に使用できる。
　基材フィルムとしては、ナイロン（Ｎｙ）６、ナイロン６６、ナイロン４６等のポリアミド樹脂、ＰＥＴ、ポリエチレンナフタレート、ポリトリメチレンテレフタレート、ポリトリメチレンナフタレート、ポリブチレンテレフタレート、ポリブチレンナフタレート等のポリエステル系樹脂、ポリ乳酸等のポリヒドロキシカルボン酸、ポリ（エチレンサクシネート）、ポリ（ブチレンサクシネート）等の脂肪族ポリエステル系樹脂に代表される生分解性樹脂、ポリプロピレン（ＰＰ）、ポリエチレン等のポリオレフィン樹脂、ポリイミド樹脂、ポリアリレート樹脂またはそれらの混合物等の熱可塑性樹脂よりなるフィルムやこれらの積層体が挙げられるが、中でも、ポリエステル、ポリアミド、ポリエチレン、ポリプロピレンからなるフィルムが好適に使用できる。これらの基材フィルムは、未延伸フィルムでも延伸フィルムでも良く、その製法も限定されるものではない。また、基材フィルムの厚さも特に限定されるものではないが、通常は１～５００μｍの範囲であればよい。
　また、基材フィルムの印刷面には、コロナ放電処理がされていることが好ましい。また、シリカ、アルミナ等が蒸着されていてもよい。 The aqueous flexographic ink for electron beam curing surface printing of the present invention is excellent in adhesion to various film substrates, and can be used for printing on thermoplastic resin films and plastic products.
As the base film, polyamide resins such as nylon (Ny) 6, nylon 66, nylon 46, etc., polyester resins such as PET, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, etc. Biodegradable resin represented by aliphatic polyester resin such as polyhydroxycarboxylic acid such as polylactic acid, polyhydroxycarboxylic acid such as polylactic acid, poly (ethylene succinate), poly (butylene succinate), polyolefin such as polypropylene (PP), polyethylene Films made of thermoplastic resins such as resins, polyimide resins, polyarylate resins or mixtures thereof, and laminates thereof can be mentioned, among which films made of polyester, polyamide, polyethylene, polypropylene Preferably it can be used. These base films may be unstretched films or stretched films, and the production method is not limited. Also, the thickness of the base film is not particularly limited, but usually, it may be in the range of 1 to 500 μm.
Moreover, it is preferable that the corona discharge process is carried out to the printing surface of a base film. In addition, silica, alumina or the like may be vapor deposited.
　本発明の電子線硬化型表刷り用水性フレキソインキは、上層から少なくとも電子線硬化型水性インキ層／フィルム層／接着剤層／アルミ箔／接着剤層／基材フィルムの順で構成される層構成で使用できる表刷り専用水性フレキソインキであリ、上層の２層である「電子線硬化型水性インキ層／フィルム層」がフィルム印刷した表刷り印刷物に相当する。また前記「電子線硬化型水性インキ層」の上層に更に「電子線硬化型水性ＯＰニス層」を設けることで、印刷物表面の耐摩性と光沢性を向上する事ができる。下層のアルミニウム／接着剤層／基材フィルムについては、予めアルミ蒸着された基材フィルムや更に多層構造を持つ高機能フィルム等を使用してもよい。 The aqueous flexographic ink for electron beam curing surface printing of the present invention is a layer composed of at least the electron beam curing aqueous ink layer / film layer / adhesive layer / aluminum foil / adhesive layer / substrate film from the upper layer The surface printing only aqueous flexographic ink which can be used in the construction, and the two layers of the upper layer, “electron beam curable aqueous ink layer / film layer” correspond to a surface printing printed matter by film printing. Further, by providing an "electron beam curable aqueous OP varnish layer" on the upper layer of the "electron beam curable aqueous ink layer", the abrasion resistance and the gloss of the printed matter surface can be improved. As the lower layer aluminum / adhesive layer / substrate film, a substrate film previously deposited with aluminum or a high functional film having a multilayer structure may be used.
　本発明の電子線硬化型表刷り用水性フレキソインキは、フレキソ印刷機を用いてプラスチックフィルムに印刷してなる印刷物表面のインキ被膜を硬化させるべく、加速器にて人工的に電子を加速した電子線（Ｅｌｅｃｔｒｏｎ　Ｂｅａｒｍ　ＥＢとも称される）線を使用する。
ＥＢ硬化方法は、印刷したインキ層がそのままインキ皮膜として形成され、紫外線硬化と異なり光重合開始剤を含まないＥＢ硬化性組成物では、設計した組成物の性質がそのままインキ皮膜の性質に反映され、ＥＢ硬化により完全に重合したインキ皮膜は、光重合開始剤などの低分子成分をほとんど含まないため、無臭又は低臭気を特徴とする。
また、ＥＢ硬化処理の場合、照射物に与える熱の影響が小さいため、薄手のフィルムに対する熱によるゆがみ、しわ、変形等が殆ど生じない。また、ＥＢ硬化処理ではライン速度毎分数１０～４００メートルあるいはそれ以上の高速処理が可能であり、紫外線硬化処理では発熱を抑制しながら同等の効果は得られない。更にＵＶランプの場合、使用時間の経過と共に光源の劣化が進み、光量が低下する事が避けられないのに対し、ＥＢ装置ではビーム電流制御により常に一定の出力を保持する事が出来る。
　使用する電子線のエネルギー強度としては３０,０００～３００,０００ｅＶであり、照射線量が５～１００ｋＧｙ・ｍ／ｍｉｎ．（キログレイ）である事が好ましい。
尚、前記「電子線硬化型水性インキ層」の上層に更に「電子線硬化型水性ＯＰニス層」を設けるべく、印刷後にロールコーター等でニス引きした場合、インキ層とＯＰニス層を
前記電子線にて同時に電子線硬化させる事ができる。 The aqueous flexo ink for electron beam curing surface printing of the present invention is an electron beam in which electrons are artificially accelerated by an accelerator to cure the ink film on the surface of a printed matter printed on a plastic film using a flexo printing machine. Use a wire (also called Electron Bearm EB).
In the EB curing method, the printed ink layer is formed as it is as an ink film, and in the case of an EB curable composition which does not contain a photopolymerization initiator unlike UV curing, the properties of the designed composition are directly reflected in the properties of the ink film. The ink film completely polymerized by EB curing is characterized by no odor or low odor since it contains almost no low molecular components such as a photopolymerization initiator.
Further, in the case of the EB curing process, since the influence of the heat given to the irradiated object is small, distortion, wrinkles, deformation and the like due to the heat to the thin film hardly occur. Further, EB curing enables high-speed processing at a line speed of 10 to 400 meters per minute or more, and UV curing does not provide the same effect while suppressing heat generation. Furthermore, in the case of a UV lamp, deterioration of the light source progresses with the lapse of use time, and it can not be avoided that the light quantity is reduced, while the EB apparatus can always maintain a constant output by beam current control.
The energy intensity of the electron beam to be used is 30,000 to 300,000 eV, and the irradiation dose is 5 to 100 kGy · m / min. It is preferable that it is (kilogray).
When the varnish is drawn by a roll coater or the like after printing in order to provide an "electron beam curable aqueous OP varnish layer" on the upper layer of the "electron beam curable aqueous ink layer", the ink layer and the OP varnish layer are Electron beam curing can be performed simultaneously with the wire.
　以下、実施例と比較例とにより、本発明を具体的に説明する。以下、「部」及び「％」は、いずれも質量基準によるものとする。 Hereinafter, the present invention will be specifically described by examples and comparative examples. Hereinafter, “parts” and “%” are all based on mass.
（電子線硬化型表刷り用水性フレキソインキ　製造方法）
　水性樹脂（Ｘ）、エチレン性二重結合を有する電子線重合性化合物（Ｙ）、顔料、及び水を含有する電子線硬化型表刷り用水性フレキソインキとして、表１の組成によるフレキソインキを調整した。
インキ１を例にとると、ＤＩＣ社製藍顔料分散ベース（ＷＦＪ　Ｒ５０７　原色藍ベース、フタロシアニン顔料を分散ベースに対し４０質量％含む）と、非反応性ウレタンディスパージョンと、脂肪族エポキシアクリレートと、（ＢＡＳＦ社製Ｌａｒｏｍａｒ　ＬＲ８７６５）ポリエチレングリコールジアクリレートと、消泡剤（ＢＹＫ製　ＢＹＫ－０１９）　とを表１に示す部数に従い十分に撹拌混合した後、粘度をザーンカップ＃５（離合社製）で１２秒（２５℃）となる様に水で調整し、印刷インキ（インキ１）を得た。該水量は、表中「残部」と示す。 (Method of producing aqueous flexo ink for electron beam curing surface printing)
A flexo ink according to the composition of Table 1 is prepared as an aqueous flexo ink for electron beam curing surface printing comprising an aqueous resin (X), an electron beam polymerizable compound (Y) having an ethylenic double bond, a pigment, and water. did.
Taking Ink 1 as an example, a pigment dispersion base manufactured by DIC (WFJ R507 primary color base, containing 40% by mass of phthalocyanine pigment based on the dispersion base), non-reactive urethane dispersion, and aliphatic epoxy acrylate, (BASF Lamarar LR8765) After sufficiently stirring and mixing polyethylene glycol diacrylate and an antifoaming agent (BYK BYK-019) according to the number of parts shown in Table 1, the viscosity is measured with Zahn cup # 5 (manufactured by Rigaku) It adjusted with water so that it might become 12 seconds (25 degreeC), and obtained printing ink (ink 1). The amount of water is shown as "remainder" in the table.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
表中、略語等は以下を表す。
水性樹脂（Ｘ）
　非反応性のウレタンディスバージョン（不揮発分３９質量％）
エチレン性二重結合を有する電子線重合性化合物（Ｙ）
　ウレタンアクリレート（ダイセル社製水系ＵＶ硬化型樹脂　固形分３５％）
　脂肪族エポキシアクリレート（ＢＡＳＦ社製Ｌａｒｏｍａｒ　ＬＲ８７６５）
　ポリエチレングリコールジアクリレート
顔料
　藍ベース（ＤＩＣ社製ＷＦＪ　Ｒ５０７　原色藍ベース　フタロシアニン顔料を分散ベースに対し４０質量％含む）
　墨ベース（ＤＩＣ社製ＷＦＪ　Ｒ８０５　墨ベース　墨ベースカーボンブラックを分散ベースに対し４０質量％含む） In the table, abbreviations etc. represent the following.
Aqueous resin (X)
Non-reactive urethane dispersion (39 mass% non-volatile matter)
Electron beam polymerizable compound (Y) having ethylenic double bond
Urethane acrylate (Water-based UV-curable resin manufactured by Daicel 35% solid content)
Aliphatic epoxy acrylate (BASF Lamarar LR 8765)
Polyethylene glycol diacrylate pigment 藍 base (consisting of 40 mass% of WFJ R507 primary color 藍 base phthalocyanine pigment manufactured by DIC based on the dispersion base)
Black base (includes 40% by mass of DIC WFJ R805 black base black base carbon black with respect to the dispersion base)
（印刷方法）
　あらかじめラミネート済みの上層から「コロナ処理ポリエチレンテレフタレート（ＰＥＴ）フィルム／接着剤層／アルミ箔／接着剤層／ポリプロピレン基材フィルム」の順で構成されたボイル・レトルト包材用積層フィルムを準備した上で、前記製造方法で得たインキ１～５をＣＩ型６色フレキソ印刷機（ＳＯＬＯＦＬＥＸ、Ｗｉｎｄｍｏｅｌｌｅｒ & Ｈｏｅｌｓｃｈｅｒ製）を用いて、それぞれ表刷り印刷した。
また、該表刷り印刷後に、ＥＢ硬化型ＯＰニスを塗布印刷する場合は、前記インキ１～５の各々のインキを印刷後、ＤＩＣ社製ＥＢ硬化型ＯＰニス（ＷＦＪ　Ｍ１０００ニス）を塗布印刷し、電子線照射を行った。
印刷後、直ちにＥＢ装置を使用しエネルギー強度が８０,０００ｅＶ、照射線量が６０ｋＧｙ・ｍ／ｍｉｎ．（キログレイ）にて電子線照射を行った。
なお、インキに使用される顔料によって照射線量が異なるため、藍ベース（ＤＩＣ社製ＷＦＪ　Ｒ５０７　原色藍ベース）を使用したインキ１，２，４，５の硬化では、アニロックス線数（ｌｉｎｅ／ｃｍ）を３１５、セルボリューム（ｃｍ３）を４．５とした。同様に、墨ベース（ＤＩＣ社製ＷＦＪ　Ｒ８０５　墨ベース）を用いた場合と、顔料を含まないＯＰニスの場合とのアニロックス線数（ｌｉｎｅ／ｃｍ）とセルボリューム（ｃｍ３）とを表２に示す。
以後、印刷済みのボイル・レトルト包材用積層フィルムを、「印刷済み積層フィルム」と称す。 (Printing method)
A laminated film for boiling and retort wrapping material was prepared in the order of "corona-treated polyethylene terephthalate (PET) film / adhesive layer / aluminum foil / adhesive layer / polypropylene base film" from the upper layer previously laminated. The inks 1 to 5 obtained by the above-mentioned production method were surface-printed and printed on a CI 6-color flexographic printing machine (SOLOFLEX, manufactured by Windmoeller & Hoelscher).
In addition, when applying and printing EB curable OP varnish after the surface printing, after printing each of the inks 1 to 5, the EB curable OP varnish (WFJ M1000 varnish) made by DIC is applied and printed. , Electron beam irradiation.
Immediately after printing, using an EB apparatus, the energy intensity is 80,000 eV and the irradiation dose is 60 kGy · m / min. Electron beam irradiation was performed at (kilo gray).
In addition, since the irradiation dose differs depending on the pigment used for the ink, in curing of the inks 1, 2, 4, and 5 using 藍 -based (WF J R507 primary color 藍 -based manufactured by DIC), the anilox line number (line / cm) And a cell volume (cm 3 ) of 4.5. Similarly, Table 2 shows the anilox line number (line / cm) and cell volume (cm 3 ) in the case of using a black base (WF-R 805 black base manufactured by DIC) and in the case of an OP varnish containing no pigment. Show.
Hereinafter, the printed laminated film for boiling and retort packaging material is referred to as "printed laminated film".
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　〔評価項目１：基材への密着性〕
印刷済み積層フィルムの印刷面に、ニチバンのセロファンテープ１８ｍｍ幅を密着させたのち、セロファンテープを垂直方向に勢いよく引き剥がし、インキの剥離度合いを目視評価した。
　　　◎：まったく剥離が見られない
　　　○：ごくわずかに剥離が見られる
　　　△：一部で剥離が見られる
　　　×：かなりの範囲で剥離する [Evaluation item 1: Adhesion to substrate]
After bringing a cellophane tape of 18 mm width from Nichiban into close contact with the printing surface of the printed laminated film, the cellophane tape was vigorously peeled off in the vertical direction, and the degree of peeling of the ink was visually evaluated.
:: no peeling observed ○: slight peeling observed :: partial peeling observed ×: peeling in a considerable range
　〔評価項目２：耐摩擦性〕
印刷済み積層フィルムの印刷面に、学振型耐摩試験機（大栄科学精器製作所製） を用い、荷重２００ｇ、１００往復の条件にて耐摩耗性試験を行い、インキ塗膜表面の傷つきの程度により評価した。
　尚、試験は印刷面同士の摩擦試験にて行った。
　　　◎：傷つきなし
　　　〇：ごく軽微な傷つきがある
　　　△：かなりの範囲で傷つきがある
　　　×：全面で傷つきがある [Evaluation item 2: Friction resistance]
The abrasion resistance test was carried out on a printed surface of the printed laminated film using a Gakushin-type abrasion tester (manufactured by Daiei Kagaku Seiki Seisakusho) under a load of 200 g under 100 reciprocating conditions. It evaluated by.
In addition, the test was done by the friction test of printing surfaces.
:: no damage 〇: very slight damage △: some damage in a considerable range x: some damage on the entire surface
　〔評価項目３：ボイル適性〕
印刷済み積層フィルムを、１２ｃｍ×１２ｃｍの大きさのパウチに製袋し、そこへ、食酢、サラダ油、ミートソースを重量比で１：１：１に配合した疑似食品４０ｇを充填密封したものを、９８℃熱水中に、６０分間のあいだ浸漬せしめるということによって、ボイル処理を行ない、その後、すぐに、印刷済み積層フィルム上の印刷物の状態の変化を観察した。
　　　◎：変化が全くない
　　　○：わずかに変化している
　　　△：かなりの範囲で変化している
　　　×：全面で変化している [Evaluation item 3: Boyl aptitude]
The printed laminated film is formed into a pouch of 12 cm × 12 cm size, and filled with sealed 40 g of simulated food containing vinegar, salad oil and meat sauce at a weight ratio of 1: 1: 1, 98 Boiling was carried out by immersing in hot water for 60 minutes, and immediately thereafter, changes in the condition of the printed matter on the printed laminated film were observed.
:: no change at all :: slight change :: change in a considerable range ×: change on the entire surface
　〔評価項目４：レトルト適性〕
印刷済み積層フィルムを、１２０ｍｍ×１２０ｍｍの大きさのパウチに製袋し、内容物として、食酢、サラダ油、ミートソースを重量比で１：１：１に配合した疑似食品４０ｇを充填密封した。作成したパウチを１２０℃、３０分間の蒸気レトルト殺菌処理をした後、その後、すぐに、印刷済み積層フィルム上の印刷物の状態の変化を観察した。
　　　◎：変化が全くない
　　　○：わずかに変化している
　　　△：かなりの範囲で変化している
　　　×：全面で変化している [Evaluation item 4: Retort aptitude]
The printed laminated film was formed into a pouch of 120 mm × 120 mm in size, and filled with 40 g of simulated food containing vinegar, salad oil and meat sauce at a weight ratio of 1: 1: 1 as contents. After the prepared pouch was subjected to steam retort sterilization treatment at 120 ° C. for 30 minutes, the change in the state of the printed matter on the printed laminated film was observed immediately thereafter.
:: no change at all :: slight change :: change in a considerable range ×: change on the entire surface
　表３に実施例１～５および比較例１に使用したインキ、ＥＢ硬化型ＯＰニス層の有無、インキ中の含水率、非反応性（非電子線硬化性）樹脂量、電子線重合性化合物量、電子線重合性化合物量１００に対する非反応性樹脂比、インキ中のＶＯＣ量、及び印刷済み積層フィルムの評価結果を記す。尚、表３中の数値は質量基準による「部」を示すものである。 Inks used in Examples 1 to 5 and Comparative Example 1 in Table 3, presence or absence of EB curable OP varnish layer, water content in ink, amount of non-reactive (non-electron beam curable) resin, electron beam polymerizable compound The amount, the non-reactive resin ratio to the amount of electron beam polymerizable compound 100, the amount of VOC in the ink, and the evaluation result of the printed laminated film are described. The numerical values in Table 3 indicate "parts" on a mass basis.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　本発明の電子線硬化型表刷り用水性フレキソインキは、インキ中のＶＯＣ量（％）を考慮する必要がなく、印刷後のエージング時間も必要としない。該インキをボイル・レトルトパウチ容器外面の印刷に用いた場合、その耐摩耗性、ボイル・レトルト適性に優れる。 The water-based flexographic ink for electron beam curing front printing of the present invention does not need to consider the amount of VOC (%) in the ink and does not require an aging time after printing. When the ink is used to print the outer surface of a boil / retort pouch container, the ink is excellent in abrasion resistance and boil / retort suitability.

Claims (9)

  1. 　水性樹脂（Ｘ）、エチレン性二重結合を有する電子線重合性化合物（Ｙ）、顔料、及び水を含有する電子線硬化型表刷り用水性フレキソインキであって、
    前記水性樹脂（Ｘ）の固形分とエチレン性二重結合を有する電子線重合性化合物（Ｙ）固形分の質量比が、（Ｘ）／（Ｙ）＝５／１００～４００／１００の範囲であることを特徴とする電子線硬化型表刷り用水性フレキソインキ。     It is an aqueous | water-based flexographic ink for electron beam-curable surface printing which contains water-based resin (X), electron beam polymeric compound (Y) which has an ethylenic double bond, a pigment, and water,
    The mass ratio of the solid content of the aqueous resin (X) and the solid content of the electron beam polymerizable compound (Y) having an ethylenic double bond is in the range of (X) / (Y) = 5/100 to 400/100 A water-based flexographic ink for electron beam-curable surface printing, characterized in that
  2. 　前記エチレン性二重結合を有する電子線重合性化合物（Ｙ）が、水溶性(メタ)アクリルモノマー及び／又は水溶性（メタ）アクリルオリゴマーである請求項１に記載の電子線硬化型表刷り用水性フレキソインキ。 The electron beam-curable surface printing according to claim 1, wherein the electron beam polymerizable compound (Y) having an ethylenic double bond is a water soluble (meth) acrylic monomer and / or a water soluble (meth) acrylic oligomer. Water-based flexographic ink.
  3. 　前記エチレン性二重結合を有する電子線重合性化合物（Ｙ）が、ポリエチレングリコールジ（メタ）アクリレートである請求項１又は２に記載の電子線硬化型表刷り用水性フレキソインキ。 The water-based flexographic ink for electron beam-curable surface printing according to claim 1 or 2, wherein the electron beam polymerizable compound (Y) having an ethylenic double bond is polyethylene glycol di (meth) acrylate.
  4. 　前記水性樹脂（Ｘ）が、非反応性水性ウレタン樹脂である請求項１～３の何れか１つに記載の電子線硬化型表刷り用水性フレキソインキ。 The water-based flexographic ink for electron beam-curable surface printing according to any one of claims 1 to 3, wherein the aqueous resin (X) is a non-reactive aqueous urethane resin.
  5. 　前記電子線のエネルギー強度が３０,０００～３００,０００ｅＶであり、照射線量が５～１００ｋＧｙ・ｍ／ｍｉｎ．（キログレイ）である請求項１～４のいずれか１つに記載の電子線硬化型表刷り用水性フレキソインキ。 The energy intensity of the electron beam is 30,000 to 300,000 eV, and the irradiation dose is 5 to 100 kGy · m / min. The water-based flexographic ink for electron beam-curable surface printing according to any one of claims 1 to 4, which is (kilo gray).
  6. 　プラスチックフィルムに請求項１～５のいずれか１つに記載の電子線硬化型表刷り用水性フレキソインキを、フレキソ印刷機を用いて印刷してなる印刷物。 A printed matter obtained by printing a water-based flexographic ink for electron beam curing surface printing according to any one of claims 1 to 5 on a plastic film using a flexographic printing machine.
  7. 　請求項６記載の印刷物と、基材とをラミネート接着剤を介してラミネートしてなる積層体。 A laminate obtained by laminating the printed matter according to claim 6 and a substrate via a laminating adhesive.
  8. 　請求項６記載の印刷物と、基材とをラミネート接着剤を介してラミネートしてなるボイル用パウチ。 A pouch for boiling formed by laminating the printed matter according to claim 6 and a substrate via a laminating adhesive.
  9. 　請求項６記載の印刷物と、基材とをラミネート接着剤を介してラミネートしてなるレトルト用パウチ。 A pouch for retort, which is obtained by laminating the printed matter according to claim 6 and a substrate via a laminating adhesive.
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WO2022209932A1 (en) * 2021-03-30 2022-10-06 Ｄｉｃグラフィックス株式会社 Laminate having printing layer of water-based liquid ink
JP7195494B1 (en) * 2021-03-30 2022-12-23 Ｄｉｃグラフィックス株式会社 Laminate with printed layer of water-based liquid ink
WO2023054026A1 (en) 2021-09-30 2023-04-06 東レ株式会社 Method for manufacturing printed matter

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