CN111108159B - Water-based flexographic ink for electron-ray-curable surface printing, and boiling/steaming pouch using same - Google Patents
Water-based flexographic ink for electron-ray-curable surface printing, and boiling/steaming pouch using same Download PDFInfo
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- CN111108159B CN111108159B CN201880061759.7A CN201880061759A CN111108159B CN 111108159 B CN111108159 B CN 111108159B CN 201880061759 A CN201880061759 A CN 201880061759A CN 111108159 B CN111108159 B CN 111108159B
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- 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
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- 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
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- 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
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- 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
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Laminated Bodies (AREA)
- Bag Frames (AREA)
- Packages (AREA)
- Wrappers (AREA)
Abstract
The present invention addresses the problem of providing a boiling/steaming pouch obtained by surface-printing on the outer surface of a pouch container using an aqueous flexographic ink for electron beam-curable surface printing, the ink having a VOC content of as much as 0% and having excellent abrasion resistance and boiling/steaming suitability. An aqueous flexographic ink for electron beam-curable surface printing, which contains an aqueous resin (X), an electron beam-polymerizable compound (Y) having an ethylenic double bond, a pigment and water, wherein the mass ratio of the solid content of the aqueous resin (X) to the solid content of the electron beam-polymerizable compound (Y) having an ethylenic double bond is (X)/(Y) in the range of 5/100 to 400/100.
Description
Technical Field
The present invention relates to an aqueous flexographic ink for surface printing which can be used in aqueous flexographic printing provided with electron beam-curable equipment, and a boiling/steaming pouch using the same.
Background
Aqueous flexographic printing is widely used for the purpose of imparting decorativeness and functionality to a printed matter.
In recent years, with the recent changes in lifestyle, such as an increase in the number of households having two employees and a number of households having one person, there are food pouches, for example, a gas replacement pouch for fast food packaging, a boiling pouch for heat treatment, and a retort pouch for heat and pressure treatment, and among them, the consumption of boiling/retort pouch for food increases year by year.
Examples of the boiling/steaming pouch include packaging materials for food and drink such as curry, hamburger, pasta sauce, soup, and rice-covered utensils, the boiling pouch is subjected to a heat treatment at a temperature of, for example, about 90 to 98 ℃ for about 30 to 60 minutes, and the steaming pouch is subjected to a heat and pressure treatment at a temperature of, for example, about 110 to 130 ℃ for about 20 to 60 minutes under pressurized conditions.
Therefore, inks used for boiling/steaming pouches are required to have durability such as abrasion resistance to withstand the above heat and pressure test and to prevent printing from being damaged during transportation and storage. In the present-day boiling/retort pouch, a laminated packaging material obtained by laminating a back-printed material using solvent-based ink with a solvent-based adhesive is generally used, but due to the improvement of food safety and environmental awareness, a packaging material which is delivered from a safer composition with a low environmental load is expected to be changed.
In order to meet such a demand, packaging materials using aqueous ink and solvent-free adhesives have been proposed, but the current situation is that: water-based inks and solvent-free adhesives using hydrophilic materials cannot achieve sufficient adhesive strength, and cannot be replaced with conventional solvent-based inks/solvent-based adhesives.
Further, although a combination of a water-based or solvent-based ink and a solvent-based or solvent-free adhesive is used, it is necessary to perform a lamination process after the back printing from the viewpoint of ink durability such as abrasion resistance, and an aging process after the lamination process is indispensable and it is not possible to transfer to a processing/filling process immediately after printing. Therefore, the conventional boiling/retort packaging material using the reverse printing has a limit in terms of shortening the delivery period.
The invention of the high-energy-ray-curable aqueous composition containing a water-soluble compound and water, wherein the water-soluble compound contains an α, β -ethylenically unsaturated radiation-polymerizable double bond, has not been sufficient in terms of abrasion resistance and boiling/retort properties necessary for retort pouches (for example, patent documents 1 to 3).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2003-147001
Patent document 2: japanese patent laid-open publication No. 2003-147230
Patent document 3: japanese laid-open patent publication No. 2008-150610
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a boiling/steaming pouch having a surface printed on the outer surface of a pouch container using an aqueous flexographic ink for electron beam-curable surface printing, the aqueous flexographic ink having a VOC (Volatile Organic compound) content in the ink of as little as 0% and having excellent abrasion resistance and boiling/steaming suitability.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the present inventors have found that the above problems can be solved by adding a particularly preferable resin, electron beam polymerizable compound, pigment, and water to a composition of an aqueous flexographic ink for surface printing which can be used in aqueous flexographic printing including an electron beam-curable device, and have completed the present invention.
The invention discovers that: the above problems can be solved even in aqueous flexographic printing by using Electron Beam (EB) -curable aqueous ink having excellent water resistance, heat resistance, abrasion resistance, and the like for surface printing of boiled/steamed pouches. That is, laminated base paper is prepared in advance, and printing is immediately performed on the surface of the base paper while receiving an order. Since Electron Beam (EB) curable aqueous ink forms a strong coating by EB irradiation, the filling/processing step can be performed immediately after the printing step is completed, and the delivery time of the boiled/steamed packaging material can be shortened.
That is, the present invention relates to an aqueous flexographic ink for electron beam-curable surface printing, which contains an aqueous resin (X), an electron beam-polymerizable compound (Y) having an ethylenic double bond, a pigment, and water, wherein the mass ratio of the solid content of the aqueous resin (X) to the solid content of the electron beam-polymerizable compound (Y) having an ethylenic double bond is (X)/(Y) in the range of 5/100 to 400/100.
The present invention also relates to an aqueous flexographic ink for electron beam-curable surface printing, 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 present invention also relates to an electron beam-curable aqueous flexographic ink for 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 an aqueous flexographic ink for electron beam-curable surface printing, wherein the aqueous resin (X) is a non-reactive aqueous urethane resin.
The present invention also relates to an electron beam-curable aqueous flexographic ink for surface printing, wherein the electron beam has an energy intensity of 30000 to 300000eV and an irradiation dose of 5 to 100 kGy.m/min.
The present invention also relates to a printed matter obtained by printing a plastic film using the aqueous flexographic ink for electron beam-curable surface printing and a flexographic printing machine.
The present invention also relates to a laminate obtained by laminating the obtained printed matter and a substrate with a laminating adhesive, and is particularly suitable for use in boiled pouches, retort pouches, and the like, which require heat resistance and water resistance.
ADVANTAGEOUS EFFECTS OF INVENTION
The aqueous flexographic ink for electron beam-curable surface printing of the present invention has a VOC content of 0% and can be used for printing on the outer surface of a retort pouch container to obtain a retort pouch having excellent boiling/retort suitability such as abrasion resistance, water resistance, and heat resistance.
Detailed Description
The aqueous flexographic ink for electron beam-curable surface printing of the present invention is characterized by containing an aqueous resin (X), an electron beam-polymerizable compound (Y) having an ethylenic double bond, a pigment and water, wherein the mass ratio of the solid content of the aqueous resin (X) to the solid content of the electron beam-polymerizable compound (Y) having an ethylenic double bond is in the range of (X)/(Y) from 5/100 to 400/100.
Here, the simplest layer structure of the retort pouch package will be described.
The most widely known layer structure is 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 (hereinafter, sometimes referred to as PET) film.
In the case where the print layer is provided on the composite film, the order of the PET film/solvent-based back printing ink layer/adhesive layer (aging is required)/aluminum foil, aluminum vapor deposition film layer/adhesive layer/polypropylene substrate film is often used from the upper layer (hereinafter, the order of "PET film/solvent-based back printing ink layer" may be referred to as the upper layer, and the order of "aluminum foil, aluminum vapor deposition film layer/adhesive layer/polypropylene substrate film" may be referred to as the lower layer), and in the production method thereof, the PET film is usually back-printed using solvent-based back printing ink, and then an adhesive is applied to the PET film, followed by bonding with the aluminum foil or aluminum vapor deposition film. In the lower layer, "aluminum foil, aluminum vapor-deposited film layer/adhesive layer/polypropylene base film", there is a highly functional film which is an integral type, and this film may be used. The lower polypropylene substrate film is not limited thereto, and other olefin-based films may be used.
In a general processing step, after back printing is performed using a solvent-based back printing ink, an adhesive is applied and laminated with other films as necessary, and aging is performed as necessary to produce a composite film, and then the composite film is formed into a pouch to obtain a retort pouch package. The process of filling the contents is performed to form a retort pouch package.
On the other hand, the aqueous flexographic ink for electron beam-curable surface printing of the present invention is an aqueous flexographic ink for surface printing which can be used in a layer configuration in which the layer configuration is an electron beam-curable aqueous ink layer/PET film layer/adhesive layer/aluminum foil, aluminum vapor deposited film layer/adhesive layer/polypropylene base film in this order from the upper layer. The electron beam-curable aqueous ink can be printed on the PET surface of a laminated film which has been laminated in advance to "a PET film layer/an adhesive layer/an aluminum foil, an aluminum vapor deposition film layer/an adhesive layer/a polypropylene base film".
When conventional solvent-based ink and adhesive for back printing are used, VOC emission in the drying step is accompanied in the printing and laminating steps. In addition, in the combination of the aqueous flexographic ink and the solvent-free binder, although VOC emission can be reduced, the binder of the ink used is an aqueous resin, and therefore sufficient adhesive strength cannot be obtained. In addition, the packaging material by the reverse printing/laminating process requires an aging process regardless of the types of ink and adhesive, and therefore, the delivery time is long and the productivity is poor.
On the other hand, in the present application, since printing can be performed on the surface of a previously prepared laminated film in which all layers except the printing layer are laminated using an Electron Beam (EB) curable aqueous ink for surface printing having excellent water resistance, heat resistance, and abrasion resistance, the steps from printing to bag making/filling can be significantly shortened as compared with the conventional steps for producing a packaging material having a laminating step after back printing.
In addition to the reduction of stock size and the reduction of delivery time by such a reduction in process time, a significant cost reduction by layer reduction and volume reduction is expected. Further, flexographic printing enables high-speed printing, and therefore higher productivity can be achieved.
Further, if an Electron Beam (EB) -curable overprint varnish layer is further applied to the surface printing layer provided with the aqueous flexographic ink for electron beam-curable surface printing of the present invention by a roll coater or the like and cured by an Electron Beam (EB), the abrasion resistance, the surface gloss, and the like can be further improved.
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 the aqueous resin (X) is essential from the viewpoint of achieving all of the abrasion resistance, water resistance, heat resistance, and the like required as boiling/retort compatibility.
Examples of suitable examples of the aqueous resin (X) include aqueous acrylic resins, aqueous styrene-maleic resins, aqueous styrene-acrylic-maleic resins, aqueous polyurethane resins, aqueous polyester resins, and other water-soluble or dispersible (emulsion and dispersion) resins of various binder resins obtained by copolymerizing acrylic acid, methacrylic acid, alkyl esters thereof, styrene, or the like as a main monomer component. Urethane resin beads or a dispersion of the beads in an aqueous solvent (also referred to as a dispersion, and also includes urethane resin dispersions, aliphatic polyurethane dispersions, and the like), or an aqueous aliphatic polyurethane dispersion can be used. Among the above resins, an aqueous urethane resin is preferable from the viewpoint of adhesion to a substrate, suitability for long-term running printing, and the like.
Further, the non-reactive aqueous urethane resin is preferable from the viewpoint of odor of ink when formed into ink and migration as a packaging material. Further, the resin composition may be used in combination with a reactive aqueous urethane resin having a (meth) acryloyl group.
As the aqueous resin (X), commercially available products can be used. In this case, the aqueous resin may be obtained in the form of a dispersion or emulsion of the aqueous resin.
The aqueous flexographic ink for electron beam-curable surface printing of the present invention requires an electron beam-polymerizable compound (Y) having an olefinic double bond. As the electron beam polymerizable compound having an ethylenic double bond, known electron beam curable monomers and oligomers can be used, and from the viewpoint of solubility in water, water-soluble (meth) acrylic monomers and water-soluble (meth) acrylic oligomers are preferable.
Specific examples of the water-soluble (meth) acrylate include, but are not limited to, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, N- (2-hydroxyethyl) acrylamide (abbreviated as "HEAA"), N- (2-hydroxyethyl) methacrylamide, N- (2-hydroxymethyl) acrylamide, N- (2-hydroxymethyl) methacrylamide, acryloylmorpholine, methylolacrylamide, dimethylacrylamide, methoxymethylacrylamide, diethylacrylamide, isopropylacrylamide, and polyethylene glycol di (meth) acrylate.
Examples of the water-soluble (meth) acrylic oligomer include CN549, CN131B, CN2285, CN 3100, CN3105, CN132, CN133, CN132 (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, LAROMERPA 9083V, romomer PO 9026V, LAROMER 8996, LAROMER 8765, and LAROMER 8986 (BASF).
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.
The mass ratio of the solid content of the aqueous resin (X) to the solid content of the electron-ray polymerizable compound (Y) having an ethylenic double bond in the aqueous flexographic ink for electron-ray curable surface printing of the present invention must be in the range of (X)/(Y) of 5/100 to 400/100.
More preferably, (X)/(Y) is 7/100 to 250/100, still more preferably (X)/(Y) is 7/100 to 50/100, and most preferably (X)/(Y) is 7/100 to 25/100.
With respect to the mass ratio, the aqueous resin is effective for imparting flexibility to the ink coating film after being irradiated with an electron beam and improving adhesion to the base material, and when the ratio of the aqueous resin portion is increased, the double bond concentration in the ink coating film is decreased, and there is a tendency for the suspense such as curing failure, rubbing resistance failure, heat resistance failure, and water resistance failure to be improved.
When the aqueous resin (X) is a commercially available product, it is basically a dispersion or emulsion of the aqueous resin, and in this case, a dry solid content of the dispersion or emulsion of the aqueous resin is used.
Examples of the pigment used in the aqueous 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.
Examples of the organic pigments include azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene pigments, perinone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, azomethine pigments, diketopyrrolopyrrole pigments, isoindoline pigments, and the like.
Examples of the inorganic pigment include carbon black, titanium oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, red iron oxide, aluminum, mica (mica), and the like. Further, a bright pigment (METASHINE; Japan Board Nitri Co., Ltd.) having a glass flake or a bulk flake as a base material and a metal or a metal oxide coated thereon can be used. From the viewpoint of cost and coloring power, titanium oxide is preferably used for the white ink, carbon black is preferably used for the black ink, aluminum is preferably used for the gold or silver ink, and mica (mica) is preferably used for the pearl ink. The aluminum is in the form of powder or paste, and is preferably used in the form of paste from the viewpoint of handling and safety, and whether it is a floating type or a non-floating type can be appropriately selected from the viewpoint of brightness and concentration.
The total amount of the pigments is an amount sufficient to ensure the concentration and coloring power of the ink, and is preferably contained in a proportion of 1 to 50% by mass relative to the total weight of the ink. Further, the coloring agent may be used alone or in combination of 2 or more.
The aqueous flexographic ink for electron beam-curable surface printing of the present invention may further contain a solvent and an auxiliary agent for other purposes.
As the above solvent, water alone or an organic solvent miscible with water may be used. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, and n-propanol; polyhydric alcohols such as propylene glycol and glycerin; and ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and ethyl carbitol.
As other auxiliary components, various waxes such as paraffin wax, polyethylene wax, PTFE wax, carnauba wax and the like for imparting friction resistance, lubricity and the like; fatty acid amides such as oleamide, stearamide and erucamide; and silicon-based and non-silicon-based defoaming agents for suppressing foaming during printing, various dispersants for improving the wettability of pigments, wetting agents for improving the wettability to substrates, and the like.
The aqueous flexographic ink for electron beam-curable surface printing according to the present invention is produced by using an Eiger Mill, a sand Mill, a Gamma Mill, an attritor and the like which are generally used for producing gravure ink and flexographic ink.
When the zeien cup #5 manufactured by clutching company is used, the viscosity of the aqueous flexographic ink for electron-beam-curable surface printing of the present invention is preferably 5 to 35 seconds, more preferably 8 to 20 seconds, at 25 ℃. When the viscosity is expressed in millipascal seconds, the viscosity may be in the range of 100 to 1000 (mPas) at 25 ℃, and more preferably 180 to 600 (mPas).
The surface tension of the aqueous flexographic ink for electron beam-curable surface printing of the present invention at 25 ℃ is preferably 25 to 50mN/m, and more preferably 33 to 43 mN/m. The lower the surface tension of the ink, the higher the wettability of the ink to a substrate such as a film, and the lower the surface tension is, the more adjacent dots are connected to each other at halftone dot portions due to wetting spread of the ink, and this tends to cause contamination of a printing surface called dot bridge. On the other hand, if the surface tension of the ink exceeds 50mN/m, the wettability of the ink with respect to a substrate such as a film tends to be reduced, which causes repulsion.
The aqueous flexographic ink for electron beam-curable surface printing of the present invention has excellent adhesion to various film substrates, and can be used for printing thermoplastic resin films and plastic products.
Examples of the base film include films and laminates thereof containing polyamide resins such as nylon (Ny)6, nylon 66 and nylon 46, polyester resins such as PET, polyethylene naphthalate, polypropylene terephthalate, polypropylene naphthalate, polybutylene terephthalate and polybutylene naphthalate, biodegradable resins represented by aliphatic polyester resins such as polylactic acid, poly (ethylene succinate) and poly (butylene succinate), polyolefin resins such as polypropylene (PP) and polyethylene, thermoplastic resins such as polyimide resins and polyarylate resins, and mixtures thereof, and films containing polyester, polyamide, polyethylene and polypropylene can be suitably used. These base films may be unstretched films or stretched films, and the production method thereof is not limited. The thickness of the base film is not particularly limited, and is usually in the range of 1 to 500. mu.m.
Further, the printed surface of the base film is preferably subjected to corona discharge treatment. Further, silicon dioxide, aluminum oxide, or the like may be vapor-deposited.
The aqueous flexographic ink for electron beam-curable surface printing of the present invention is an aqueous flexographic ink for surface printing that can be used in a layer configuration in which at least an electron beam-curable aqueous ink layer/film layer/adhesive layer/aluminum foil/adhesive layer/base film is formed in this order from the upper layer, and the two layers of the upper layer, i.e., "electron beam-curable aqueous ink layer/film layer", correspond to a surface print obtained by film printing. Further, by further providing an "electron beam-curable aqueous OP varnish layer" on the "electron beam-curable aqueous ink layer", the abrasion resistance and gloss of the surface of the printed matter can be improved. As the aluminum/adhesive layer/base material film of the lower layer, a base material film formed by aluminum deposition in advance, a high-functional film further having a multilayer structure, or the like can be used.
In order to cure the ink coating on the surface of a printed matter obtained by printing the aqueous flexographic ink for Electron beam-curable surface printing of the present invention on a plastic film using a flexographic printing machine, an Electron beam obtained by artificially accelerating electrons using an accelerator (also referred to as Electron beam EB) is used.
The EB curing method is characterized in that the printed ink layer is formed directly as an ink coating, and unlike ultraviolet curing, the properties of the designed composition are directly reflected in the properties of the ink coating in the EB curable composition containing no photopolymerization initiator, and the ink coating completely polymerized by EB curing contains almost no low-molecular components such as photopolymerization initiator, and therefore, has no or low odor.
In the EB curing treatment, the influence of heat applied to the irradiated object is small, and therefore, warpage, wrinkles, deformation, and the like due to heat applied to the film are hardly caused. In addition, in the EB curing treatment, a high-speed treatment with a linear velocity of 10 to 400 m/min or more can be performed, and in the ultraviolet curing treatment, the same effect cannot be obtained while suppressing heat generation. Further, in the case of the UV lamp, deterioration of the light source occurs with the lapse of the use time, and the decrease of the light amount cannot be avoided, whereas the EB device can always maintain a constant output by the electron beam current control.
Preferably, the energy intensity of the electron beam used is 30000-300000 eV, and the irradiation dose is 5-100 kGy.m/min.
In order to further provide an "electron beam-curable aqueous OP varnish layer" on the "electron beam-curable aqueous ink layer", when the varnish is drawn out by a roll coater or the like after printing, the ink layer and the OP varnish layer can be simultaneously electron beam-cured by the electron beam.
Examples
The present invention will be described in detail below with reference to examples and comparative examples. Hereinafter, "part(s)" and "%" are based on mass.
(method for producing Water-based flexographic ink for Electron Beam-curing surface printing)
Flexographic inks having the compositions shown in table 1 were prepared as aqueous flexographic inks for electron beam-curable surface printing, each aqueous flexographic ink containing an aqueous resin (X), an electron beam-polymerizable compound (Y) having an ethylenic double bond, a pigment and water.
Taking ink 1 as an example, a blue pigment dispersion base (WFJ R507 primary color blue base containing 40 mass% of phthalocyanine pigment with respect to the dispersion base), a non-reactive urethane dispersion, an aliphatic epoxy acrylate, (Laromar LR8765) polyethylene glycol diacrylate manufactured by BASF) and an antifoaming agent (BYK-019 manufactured by BYK) were sufficiently mixed in the parts shown in table 1, and then the viscosity was adjusted with water so as to reach 12 seconds (25 ℃) by zeitan cup #5, manufactured by clutching company, to obtain a printing ink (ink 1). This amount of water is shown as "balance" in the table.
[ Table 1]
In the table, the abbreviations and the like have the following meanings.
Water resin (X)
Non-reactive urethane dispersion (nonvolatile content: 39 mass%)
Electron-ray polymerizable compound (Y) having olefinic double bond
Urethane acrylate (35% as solid content of aqueous UV curable resin manufactured by Dailuo Co., Ltd.)
Aliphatic epoxy acrylate (Laromar LR8765 manufactured by BASF Co., Ltd.)
Polyethylene glycol diacrylate
Pigment (I)
Blue matrix (WFJ R507 color blue matrix manufactured by DIC corporation containing 40 mass% of phthalocyanine pigment based on dispersion matrix)
Black matrix (WFJ R805 Black matrix manufactured by DIC corporation, 40% by mass of black matrix carbon black based on the dispersed matrix)
(printing method)
A laminated film for boiling/retort packaging material, which was laminated in advance in the order of "corona-treated polyethylene terephthalate (PET) film/adhesive layer/aluminum foil/adhesive layer/polypropylene base film" from the upper layer, was prepared, and the inks 1 to 5 obtained by the above-described production method were each subjected to surface printing using a CI type six-color flexographic printing machine (sold by SOLOFLEX, windmeyer & Hoelscher).
When EB-curable OP varnish is applied and printed after the surface printing, the above-described inks 1 to 5 are printed, and then EB-curable OP varnish (WFJ M1000 varnish) manufactured by DIC corporation is applied and subjected to electron beam irradiation.
Immediately after printing, electron beam irradiation was performed using an EB device under conditions of an energy intensity of 80000eV and an irradiation dose of 60kGy · m/min (kilogray).
The irradiation dose varies depending on the pigment used in the ink, and in curing of inks 1, 2, 4, and 5 using a blue matrix (WFJ R507 primary color blue matrix manufactured by DIC corporation), the number of cross hatching lines (line/cm) was 315, and the cell volume (cm) was set to be3) Set to 4.5. Similarly, the number of cross hatching lines (line/cm) and the cell volume (cm) were measured for the case of using a black matrix (WFJ R805 Black matrix manufactured by DIC Co., Ltd.) and the case of using an OP varnish containing no pigment3) Shown in table 2.
Hereinafter, the printed laminated film for boiling/retort packaging material is referred to as "printed laminated film".
[ Table 2]
[ evaluation item 1: adhesion to substrate ]
After an 18mm wide scotch tape of NICHIBAN corporation was adhered to the printing surface of the printed laminated film, the scotch tape was peeled off at once in the vertical direction, and the degree of ink peeling was visually evaluated.
Very good: peeling was not observed at all
O: peeling was slightly observed
And (delta): peeling was partially observed
X: peeling occurs in a wide range
[ evaluation item 2: resistance to rubbing ]
The printed surface of the printed laminated film was subjected to an abrasion resistance test under a load of 200g and 100 cycles using a chemical vibration abrasion tester (manufactured by Daorhiki Seisakusho Co., Ltd.), and the degree of damage on the ink coating surface was evaluated.
The test was performed by a rubbing test of the printed surfaces.
Very good: without damage
O: there was very slight injury
And (delta): over a wide range of damage
X: general injury
[ evaluation item 3: suitability for boiling ]
The printed laminated film was made into a 12cm × 12 cm-sized pouch, 40g of a simulated food prepared by blending vinegar, salad oil, and minced meat paste at a weight ratio of 1: 1 was filled and sealed therein, and the pouch was immersed in hot water at 98 ℃ for 60 minutes to carry out boiling treatment, and then the state change of the printed matter on the printed laminated film was immediately observed.
Very good: is not changed at all
O: slightly changed
And (delta): changes within a wide range
X: changes all over
[ evaluation item 4: suitability for cooking)
The printed laminated film was made into 120mm × 120mm small bags, and 40g of a simulated food prepared by mixing vinegar, salad oil, and minced meat paste at a weight ratio of 1: 1 was filled and sealed as contents. The pouch thus produced was subjected to steam-boiling sterilization at 120 ℃ for 30 minutes, and then immediately thereafter, the state change of the printed matter on the printed laminated film was observed.
Very good: is not changed at all
O: slightly changed
And (delta): changes within a wide range
X: changes all over
Table 3 shows the inks used in examples 1 to 5 and comparative example 1, the presence or absence of an EB curable OP varnish layer, the water content in the ink, the amount of non-reactive (non-electron-ray curable) resin, the amount of electron-ray polymerizable compound, the ratio of non-reactive resin to the amount of electron-ray polymerizable compound 100, the amount of VOC in the ink, and the evaluation results of the printed laminated film. In addition, the numerical values in table 3 represent "parts" on a mass basis.
[ Table 3]
The aqueous flexographic ink for electron beam-curable surface printing of the present invention does not require consideration of the amount of VOC (%) in the ink, nor aging time after printing. When the ink is used for printing on the outer surface of a boiling/steaming pouch container, the ink is excellent in abrasion resistance and boiling/steaming suitability.
Claims (6)
1. An aqueous flexographic ink for electron beam-curable surface printing, which comprises 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) to the solid content of the electron-ray polymerizable compound (Y) having an ethylenic double bond is (X)/(Y) in the range of 5/100 to 400/100,
the aqueous resin (X) is a non-reactive aqueous urethane resin,
the electron beam polymerizable compound (Y) having an ethylenic double bond is polyethylene glycol di (meth) acrylate,
the viscosity of the aqueous flexographic ink for electron-beam-curable surface printing was 5 to 35 seconds at 25 ℃ when Zeitn cup #5 manufactured by Seiko corporation was used.
2. The aqueous flexographic ink for electron beam-curable surface printing according to claim 1, which is an aqueous flexographic ink for electron beam-curable surface printing,
the energy intensity of the electron beam used in the electron beam curing is 30000eV to 300000eV, and the irradiation dose is 5 kGy.m/min to 100 kGy.m/min, wherein kGy is kilogray.
3. A printed matter obtained by printing the aqueous flexographic ink for electron beam-curable surface printing according to claim 1 or 2 onto a plastic film using a flexographic printing machine and then curing the ink coating on the surface of the plastic film by electron beam irradiation.
4. A laminate obtained by laminating the printed matter according to claim 3 and a substrate with a laminating adhesive.
5. A boiled pouch obtained by laminating the printed matter according to claim 3 and a base material with a laminating adhesive.
6. A retort pouch comprising the printed matter according to claim 3 and a substrate laminated with a laminating adhesive.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017192646 | 2017-10-02 | ||
| JP2017-192646 | 2017-10-02 | ||
| PCT/JP2018/035303 WO2019069736A1 (en) | 2017-10-02 | 2018-09-25 | Electron beam-curable water-based flexo ink for surface printing and boilable retort pouch using same |
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| Publication Number | Publication Date |
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| CN111108159A CN111108159A (en) | 2020-05-05 |
| CN111108159B true CN111108159B (en) | 2021-06-11 |
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| CN201880061759.7A Active CN111108159B (en) | 2017-10-02 | 2018-09-25 | Water-based flexographic ink for electron-ray-curable surface printing, and boiling/steaming pouch using same |
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| Country | Link |
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| JP (1) | JP6557799B1 (en) |
| CN (1) | CN111108159B (en) |
| AU (1) | AU2018344119B9 (en) |
| WO (1) | WO2019069736A1 (en) |
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| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1732238A (en) * | 2002-12-27 | 2006-02-08 | 太阳化学公司 | Radiation curable aqueous compositions |
| CN101945907A (en) * | 2008-03-18 | 2011-01-12 | 氰特表面技术有限公司 | The aqueous radiation curable polyurethane composition |
| CN102119183A (en) * | 2008-08-12 | 2011-07-06 | 巴斯夫欧洲公司 | Use of aqueous polyurethane dispersions in printing inks and corresponding printing process |
| CN103436095A (en) * | 2013-09-08 | 2013-12-11 | 鲁继烈 | Ultraviolet-curing water-based inkjet ink |
| CN104507977A (en) * | 2012-06-15 | 2015-04-08 | 太阳化学公司 | Lithographic offset inks with water and filler content |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0379362B2 (en) * | 1979-08-31 | 1991-12-18 | Suteibondo Pty Ltd | |
| JPH08218016A (en) * | 1995-02-09 | 1996-08-27 | Canon Inc | Ink for ink-jet printing, device for producing ink-jet print using the same and production of ink-jet print |
| JPH11100528A (en) * | 1997-09-26 | 1999-04-13 | Dainippon Ink & Chem Inc | Active energy ray curable water-borne composition |
| US6772683B2 (en) * | 2002-02-19 | 2004-08-10 | Sun Chemical Corporation | Method and apparatus for wet trapping with energy-curable flexographic liquid inks |
| JP2005225083A (en) * | 2004-02-13 | 2005-08-25 | Toyo Ink Mfg Co Ltd | Printing structure |
| US20070263060A1 (en) * | 2005-01-14 | 2007-11-15 | Mikhail Laksin | Hybrid Energy Curable Solvent-Based Liquid Printing Inks |
| JP6875831B2 (en) * | 2016-11-09 | 2021-05-26 | サカタインクス株式会社 | Water-based flexographic printing ink composition for front printing |
-
2018
- 2018-09-25 CN CN201880061759.7A patent/CN111108159B/en active Active
- 2018-09-25 AU AU2018344119A patent/AU2018344119B9/en active Active
- 2018-09-25 JP JP2019524478A patent/JP6557799B1/en active Active
- 2018-09-25 WO PCT/JP2018/035303 patent/WO2019069736A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1732238A (en) * | 2002-12-27 | 2006-02-08 | 太阳化学公司 | Radiation curable aqueous compositions |
| CN101945907A (en) * | 2008-03-18 | 2011-01-12 | 氰特表面技术有限公司 | The aqueous radiation curable polyurethane composition |
| CN102119183A (en) * | 2008-08-12 | 2011-07-06 | 巴斯夫欧洲公司 | Use of aqueous polyurethane dispersions in printing inks and corresponding printing process |
| CN104507977A (en) * | 2012-06-15 | 2015-04-08 | 太阳化学公司 | Lithographic offset inks with water and filler content |
| CN103436095A (en) * | 2013-09-08 | 2013-12-11 | 鲁继烈 | Ultraviolet-curing water-based inkjet ink |
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| AU2018344119A1 (en) | 2020-04-09 |
| JP6557799B1 (en) | 2019-08-07 |
| CN111108159A (en) | 2020-05-05 |
| AU2018344119B9 (en) | 2020-10-08 |
| WO2019069736A1 (en) | 2019-04-11 |
| JPWO2019069736A1 (en) | 2019-11-14 |
| AU2018344119B2 (en) | 2020-10-01 |
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